A T‐Shaped μ 3 ‐Oxido Trinuclear Iron Cluster with High Easy‐Plane Anisotropy: Structural and Magnetic Characterization

2008

The synthesis, crystal structure and magnetochemical characterization of a new μ-oxido trinuclear iron cluster (oldnomenclature: μ-oxo trinuclear iron cluster), [Fe3(μ3-O)(μ2-CH3O)2(μ2-CH3COO)2(phen)2Cl3], is reported. The reaction of hydrated FeCl3 with sodium acetate and 1,10-phenanthroline in a mixture of methanol and acetonitrile afforded crystals suitable for X-ray crystallographic determination. The new compound crystallizes in the tetragonal I41/a space group (a = b = 13.6322 A, c = 37.3538 A, Z = 8, V = 6941.7 A3). The core of the complex is an isosceles triangle bridged by a μ3-O ion with a rare T-shaped geometry. The chloride ions are bound terminally, and the phenanthroline ligan…

Structure and Electronic Properties of an Expanded Terpyridine Complex of Nickel(II) [Ni(ddpd)2](BF4)2

2018

Polynuclear copper(II) complexes with hexadentate Schiff base directed by the counter ion. Syntheses, crystal structures and magnetic properties

2018

Abstract Four new complexes, [Cu 9 L 6 ( µ 3 -ClO 4 ) 2 ](ClO 4 ) 4 ·4CHCl 3 1 , [Cu 3 L 2 (H 2 O) 2 ](ClO 4 ) 2 ·3H 2 O 2 , [Cu 6 L 4 (N 3 ) 2 ](ClO 4 ) 2 3 and [Cu 2 L(CH 3 COO) 2 ] 4 , where H 2 L stands for the Schiff base N , N ′-bis[(2-hydroxybenzilideneamino)-propyl]-piperazine, were obtained and structurally characterized. Compounds 1 , 2 and 3 contain the Cu 3 L 2 2+ entities in which L 2− acts in an unsymmetrical mode with N 3 O donor set wrapped around marginal copper(II) and with the remained NO sets bound to the central copper ion. The marginal copper(II) ions are in distorted square pyramidal environment, whereas that of the central one is square planar. In 1 , the peripheral …

Magnetic Study of a Pentanuclear {Co 2 III Co 3 II } Cluster with a Bent {Co II 3 } Motif

2014

We have synthesised and structurally characterised a new pentanuclear mixed-valent cobalt cluster of formula [CoII3CoIII2(OH)2(piv)6(L)2(H2O)4] (piv = trimethylacetate, H2L = salicylideneanthranillic acid) from reaction of a dinuclear cobalt pivalate precursor with a Schiff base type ligand under mild reaction conditions. The core structure can be conveniently described as two fused Co3–μ3–OH triangles with a strict unique sharing vertex point. A complete picture of the magnetic behaviour of this compound is presented. Through combined use of susceptibility, magnetisation, and EPR data as well as broken-symmetry DFT calculations, we have supported the magnetic data that show weak and anisot…

Nitronyl Nitroxide Radicals Linked to Exchange‐Coupled Metal Dimers – Studies Using X‐ray Crystallography, Magnetic Susceptibility Measurements, EPR …

2009

To study long-range magnetic interactions between exchange-coupled metal centers and a radical moiety coordinated through a peripheral group, three new homodimetallic complexes with MnII, CoII, and ZnII bridged by a nitronyl nitroxide (NIT) substituted benzoate ligand with the structure [(NIT-C6H4-COO)M2(LR)](ClO4)2 {M = MnII, CoII, and ZnII; NIT = nitronyl nitroxide and LR = N,N,N′,N′-tetrakis(2-benzimidazolylalkyl)-2-hydroxy-1,3-diaminopropane} have been prepared and studied by X-ray crystallography, magnetic susceptibility measurements, EPR spectroscopy, and density functional theory calculations. For comparison, related complexes with MnII and CoII bridged by a diamagnetic nitrobenzoate…

{CoIII2DyIII2} single molecule magnet with two resolved thermal activated magnetization relaxation pathways at zero field

2014

The new complex [CoIII2DyIII 2(OMe)2(teaH)2(Piv)6] in the {CoIII2DyIII2} family, shows two well resolved thermal activated magnetization relaxation pathways under AC experiments in zero DC field. Fitted crystal field parameters suggest that the origin of these two pathways relies on two different excited mJ sub-levels. Fil: Funes, Víctor Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina …

Synthesis, Structural and Spectroscopic Characterization of Cr III , Fe III , Co III , Ni II and Cu II Complexes with an Asymmetric 1,3,4‐Thiadiazole…

2016

The reaction of the new asymmetric 1,3,4-thiadiazole-based ligand 2-[(5-ethylthio-1,3,4-thiadiazol-2-yl)hydrazonomethyl]phenol (H1ETHP) with various third-row transition metal salts resulted in the formation of six new mononuclear complexes [Cr(ETHP)2]ClO4 (1), [Fe(ETHP)2][FeCl4] (2), [Co(ETHP)(ETHP–H)] (3), [Ni(ETHP)(H1ETHP)]Cl (4), [Ni(ETHP)(H1ETHP)](ClO4) (5), [Ni(ETHP)(H1ETHP)]Br (6), and one tetranuclear complex [Cu2Cl3(ETHP)(H1ETHP)]2 (7). H1ETHP and all complexes have been analyzed by single crystal X-ray diffraction. Structural analysis of 1–6 reveals complexes of the [ML2]n+-type (n = 0,1), in which the mono anionic ligand ETHP coordinates in a tridentate NNO fashion via its imine,…

Metallacrown Complexes Reaching the Nanosize Regime

2018

Abstract The chapter discusses the merit of metallacrown complexes to achieve multifunctional and multidimensional molecular materials. It introduces basic design strategies for discrete metallacrown complexes and discusses the predictability of molecular properties. Thereafter, it reviews two of the most outstanding molecular properties of metallacrown complexes, namely, the magnetic and luminescence characteristics. Most interestingly, for metallacrown complexes, such properties could be combined in one single molecule, giving rise to stable “multifunctional” molecular materials. Moreover, MCs are suitable building blocks to construct multidimensional coordination polymers. The chapter pr…

Fe II Complexes with Triple N 1, N 2‐Triazole Bridge Schiff Base Ligand: Antiferromagnetic Dimer vs. Spin Conversion Trimer

2018

Titelbild: Direct CH Metalation with Chromium(II) and Iron(II): Transition-Metal Host / Benzenediide Guest Magnetic Inverse-Crown Complexes (Angew. …

2009

Chrom und Eisen als die neuesten Erganzungen des Konzepts der alkalimetallvermittelten Metallierung stellen J. Klett, R. E. Mulvey et al. in ihrer Zuschrift auf S. 3367 ff. vor. Das elektropositivere Natrium ist wesentlich fur die Reaktion, doch das weniger elektropositive Chrom oder Eisen ist es, das Benzol tatsachlich deprotoniert. Diese neuartige Reaktivitat kann mit einem Schachspiel verglichen werden, bei dem die Konigin (Na) dem Konig Schach bietet und der Springer (Cr, Fe) Matt setzt.

First Cobalt(II) Spin Crossover Compound with N4S2-Donorset

2020

Herein we report the synthesis and characterization of a novel bis-tridentate 1,3,4-thiadiazole ligand (L = 2,5-bis[(2-pyridylmethyl)thio]methyl-1,3,4-thiadiazole). Two new mononuclear complexes of the type [MII(L)2](ClO4)2 (with M = FeII (C1) and CoII (C2)) have been synthesized, containing the new ligand (L). In both complexes the metal centers are coordinated by an N4S2-donorset and each of the two ligands is donating to the metal ion with just one of the tridentate pockets. The iron(II) complex (C1) is in the low spin [LS] state below room temperature and shows an increase in the magnetic moment only above 300 K. In contrast, the cobalt(II) complex (C2) shows a gradual spin crossover (S…

Rational design of covalently bridged [FeIII2MIIO] clusters

2010

We are reporting the first supramolecular dimeric units of basic carboxylates. The neutral [FeIII 2MIIO] motif for different 3d M metals is covalently bound through 2,2′-bipyrimidine. We have structurally characterized the hexanuclear clusters and the related trinuclear building blocks. Their magnetic properties have been fully analyzed and DFT calculations have been performed as a supplementary tool. All results evidence a weak antiferromagnetic interaction through the bpym bridge between isolated spin ground states (in some examples) arising from intra-Fe 2MO core exchange couplings. Fil: Alborés, Pablo. Johannes Gutenberg Universitat Mainz; Alemania. Consejo Nacional de Investigaciones C…

Functionalized phosphonates as building units for multi-dimensional homo- and heterometallic 3d-4f inorganic-organic hybrid-materials.

2016

Using the multifunctional ligand H4L (2,2'-bipyridinyl-5,5'-diphosphonic acid), a new family of inorganic-organic hybrid-materials was prepared. The ligand shows a very high flexibility regarding the coordination mode, leading to a large structural diversity. The compounds 1a, 1b ([M(H2L)(H2O)4]·2.5H2O; M = Co(2+) (a), Ni(2+) (b)), 2 ([Gd2(H2H'L)2(H2H'2L)(H2O)6]Cl4·14H2O), 3a, 3b, 3c ([MCo(iii)(H2L)3(H2O)2]·6.5H2O; M = Gd(3+) (a), Dy(3+) (b) and Tb(3+) (c)), and 4 ([GdNi(ii)(H2L)3(H2O)3]NaCl·6H2O) were isolated and characterized with single crystal X-ray diffraction. Depending on the used metal ions and on the stoichiometry, either discrete entities (0D), extended 2D layers or 3D frameworks…

Mononuclear Mn(III) and dinuclear Mn(III,III) Schiff base complexes: Influence of π–π stacking on magnetic properties

2012

Abstract Synthesis of a mononuclear Mn(III) (1) and a dinuclear Mn(III, III) (2) complex of a tetradentate N2O2 donor Schiff base ligand with ancillary carboxylate ligands are reported. Complex 1 crystallizes in the monoclinic space group C2/c, complex 2 in the triclinic space group P-1. In both complexes the central Mn(III) ions are hexacoordinated having a distorted octahedral MnN2O4 coordination environment. Intermolecular hydrogen bonding and strong π–π stacking in both 1 and 2 leads to dimerization of 1 and formation of a syn–anti one-dimensional chain for 2. Magnetic properties of 1 and 2 are reported. Both complexes show very weak intermolecular antiferromagnetic interaction. Most in…

One dimensional Mn(III) Schiff-base complex organization through very strong symmetrical H-bond interaction

2016

Abstract We are reporting the structural and magnetic characterization of a Mn(III) mononuclear complex based on a Schiff-base ligand with carboxylate pendant arm. Very strong symmetric H-interaction drives a one dimensional organization of this complex, densely packed through C–H⋯π further interactions. Low temperature magnetic behaviour appears governed by local ion zero field splitting obscuring any possible weak exchange interaction through the symmetric H-bond pathway.

Synthesis, structural characterization and magnetic behaviour of a family of [CoIII2LnIII2] butterfly compounds

2017

We have successfully prepared and structurally characterized a family of butterfly-like [Co2 IIILn2 III] complexes where all magnetic properties are due to the Ln(iii) ions. The complexes with Ln = Tb(1), Dy(2), Ho(3), Er(4) and Yb(5) are iso-structural. An exception is the complex with Ln = Gd(6) which strings in a one dimensional chain. The structural similarity together with the high tendency of the crystallites to align under an applied magnetic field allowed an overall DC magnetic data treatment to extract phenomenological crystal field parameters and hence to determine the ground state multiplet energy level splitting. The Dy(iii) member is the only one showing slow relaxation of magn…

Spin transition in three-dimensional bridged coordination polymers of iron(II)–urea-triazoles

2008

Abstract Three-dimensional spin-crossover (SCO) networks of [Fe 2 ( n -Rdubtrz) 3 ](X) 4  ·  n H 2 O ( n -R = (CH 2 ) y , y  = 4, 6, 8, 12; du = diurea; btrz = bis-triazole; X = BF 4 - , ClO 4 - , triflate, tosylate) coordination polymers are prepared by reaction of bridging aliphatic bis-urea triazoles ( n -Rdubtrz) with the iron-salts (FeX 2 ). Investigations of the properties are supported by studies of one-dimensional compounds of [Fe(Rtrzu) 3 ](X) 2 (R =  n -propyl, t -butyl; trzu = urea triazole). Characterization of the complexes is carried out with IR-spectroscopy, elemental analysis, TGA and atomic absorption spectroscopy. SCO-behaviour of all complexes is inspected by magnetic sus…

Bis[(trimethylsilyl)methyl]manganese: Structural Variations of Its Solvent-Free and TMEDA-, Pyridine-, and Dioxane-Complexed Forms

2009

First synthesized in 1976 and recently taking on a new significance as a key precursor to heterobimetallic alkali-metal-manganese(II) complexes, bis[(trimethylsilyl)methyl] manganese has been structurally characterized by X-ray crystallography. It forms a polymeric chain structure of formula [{Mn(CH2SiMe3)(2)}(infinity)], 1, in which distorted tetrahedral, spiro Mn atoms are linked together via mu(2)-bonding alkyl ligands. The structure is notable for displaying two distinct categories of Mn-C bond lengths with a mean size differential of 0.225 angstrom and for being the first fully crystallographically characterized polymeric manganese(II) dialkyl compound. Magnetic measurements of 1 indic…

Impact of molecule-based magnetic materials: A critical outlook

2009

Abstract A critical outlook of the field of molecular magnetic materials is presented. This article is inspired by an international symposium devoted to the “ Design, Characterization and Modelling of Molecule-Based Magnetic Materials (DCM4-II)” that took place at Strasbourg (France), from May 28th to June 1st, within the E-MRS 2007 Spring Meeting (Symposium R) organized by the European Materials Research Society in collaboration with the European Science Foundation . A series of papers linked to this symposium are published in this issue and in the previous issue (Volume 11, Issue 4) of Solid State Sciences.

Exploring the Slow Relaxation of the Magnetization in CoIII -Decorated {DyIII 2 } Units

2016

We have prepared and structurally characterized a new member of the butterfly-like {CoIII 2DyIII 2} single-molecule magnets (SMMs) through further CoIIIdecoration, with the formula [CoIII 4DyIII 2(OH)2(teaH)2(tea)2(Piv)6] (teaH3=triethanolamine; Piv=trimethylacetate or pivalate). Direct current (DC) susceptibility and magnetization measurements were performed allowing the extraction of possible crystal-field parameters. A simple electrostatic modeling shows reasonable agreement with experimental data. Alternating current (AC) susceptibility measurements under a zero DC field and under small applied fields were performed at different frequencies (i.e., 10–1500 Hz) and at low temperatures (i.…

Hexanuclear copper(ii) cage with {Cu3O⋯H⋯OCu3} core supported by a dicompartmental oxime ligand with m-xylyl spacer: synthesis, molecular structure a…

2010

A new dicompartmental dioxime ligand (H(2)L) with m-xylyl spacer between the donor sites has been synthesised by Schiff-base condensation of α,α'-diamino-m-xylene and diacetyl monooxime. The ligand reacts with copper(ii) salts giving rise to hexanuclear tricationic copper(II) cage complexes [Cu(II)(6)(μ(3)-O···H···O-μ(3))L(3)(H(2)O)(6)]X(3) (X = BF(4), 1a; X = ClO(4), 1b). The complexes have been characterised by different analytical and spectroscopic techniques and confirmed the hexanuclear structure even in solution. Single crystal X-ray diffraction studies of both the complexes revealed a very similar core structure with three dicompartmental ligands supporting two triangular Cu(3)O core…

Titelbild: Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) …

2019

Two new supramolecular architectures of singly phenoxo-bridged copper(II) and doubly phenoxo-bridged manganese(II) complexes derived from an unusual …

2009

International audience; Two new coordination complexes {[(L)Cu2('-L)(NO3)(CH3OH)0.3(H2O)0.7]·NO3}[Cu(L)(NO3)(CH3OH)] (1) and [Mn2(-L)2(H2O)(1-N3)2(CH3OH)] (2) derived from (E)-N-(2-hydroxy-3-methoxybenzylidene)acetohydrazide [LH] have been synthesized. The new potentially tetradentate ONOO donor hydrazone ligand [LH] has shown considerable metal ion selective phenoxo bridging in 1 and 2. It has coordinated copper(II) ions in its tridentate as well as in tetradentate fashion whereas for manganese(II) ions it solely showed its tetradentate character. In 1 the two adjacent pentacoordinate copper(II) centers are connected by a rare single phenoxo linkage of the hydrazone ligand whereas 2 is a d…

Sodium-mediated manganation: direct mono- and dimanganation of benzene and synthesis of a transition-metal inverse-crown complex.

2007

Inside out approach: Twofold deprotonation of benzene by a sodium monoalkyl bisamido manganate(II) reagent derived from BuNa, 2,2,6,6-tetramethylpiperidine, and Mn(CH2SiMe3)2 has produced the first inverse-crown complex in which the transition-metal atoms are incorporated in the host (see X-ray structure, blue N, green Na, purple Mn). Variable-temperature magnetization measurements show that the complex is antiferromagnetic.

Element-specific magnetic properties of mixed 3d−4f metallacrowns

2018

Single molecule magnets comprising rare earth metals are of high interest due to the unquenched orbital moments of the rare earth ions that result in a large energy barrier for magnetization reversal. We investigate the magnetic properties of polynuclear $3d\text{\ensuremath{-}}4f15$-MC-5 metallacrowns using x-ray magnetic circular dichroism of powder samples at a temperature of 7 K in a magnetic field of 7 T. The sum rule analysis reveals element-specific spin and orbital moments. The magnetic moments of the $3d$ transition metal Ni(II) ions are coupled antiferromagnetically to each other and contribute only little to the total molecular moment. The spin and orbital moments of the rare ear…

A distorted honeycomb motif in divalent transition metal compounds based on 4-phosphonbenzoic acid and exchange coupled Co(II) and Cu(II): synthesis,…

2013

The first example of a two-dimensional inorganic hybrid material with cobalt as an open-shell transition metal ion and 4-phosphonbenzoic acid as a linker is presented together with its copper analogue. For both metal ions the inorganic part consists of edge-sharing metal–oxygen octahedra leading to a metal honeycomb motif. The magnetic properties of the cobalt compound are reported together with those of the corresponding copper compound based on the remarkably six-coordinated copper(II) ions.

A Family of Dinuclear Iron(II) SCO Compounds Based on a 1,3,4‐Thiadiazole Bridging Ligand (Eur. J. Inorg. Chem. 22/2015)

2015

Triple bridged μ-phenoxo-bis(μ-carboxylate) and double bridged μ-phenoxo-μ1,1-azide/μ-methoxide dicopper(II) complexes: Syntheses, structures, magnet…

2013

Abstract The work in this paper presents syntheses, characterization, crystal structures, catecholase activity, electrospray ionization mass spectroscopy (ESI-MS positive), and magnetic properties of seven triple bridged μ-phenoxo-bis(μ-carboxylate) dicopper(II) complexes [CuII2L(μ-HCOO)2](ClO4)·CH3OH (1), [CuII2L(μ-CH3COO)2](ClO4) (2), [CuII2L(μ-CCl3COO)2(H2O)](ClO4) (3), [CuII2L(μ-CH3CH2COO)2](ClO4) (4), [CuII2L(μ-CH3CH2CH2COO)2](ClO4) (5), [CuII2L(μ-PhCOO)2](ClO4)·CH3CN (6) and [CuII2L(μ-o-ClPhCOO)2](ClO4) (7), one double bridged μ-phenoxo-μ1,1-azide system [CuII2L(μ1,1-N3)(N3)2] (8) and one double bridged μ-phenoxo-μ-methoxide system [CuII2L(μ-OCH3)(NCO)2] (9), derived from a new dinucl…

An intramolecular antiferromagnetically coupled pentanuclear homoleptic Mn(II) cluster: Synthesis, crystal structure, spectral and magnetic property

2013

Abstract A pyrazole based ditopic ligand 5(E)-5-methyl-N′-(pyridin-2-ylmethylene)-1H-pyrazole-3-carbohydrazide (PzOPyH), prepared by the reaction between 5-methylpyrazole-3-carbohydrazide and pyridine-2-carbaldehyde, reacts with Mn(ClO4)2·6H2O to form a self-assembled, antiferromagnetically coupled alkoxide bridged pentanuclear Mn(II) homoleptic cluster complex [Mn5(PzOPy)6](ClO4)4 (1). The complex has a central Mn5(μ-O6) core involving six ligand molecules. This pentanuclear core has a trigonal bipyramidal arrangement of Mn(II) atoms, where, the axial metal centers (Mn2 and Mn_2) have a N3O3 chromophore and the equatorial centers (Mn1, Mn_1 and Mn3) have N4O2 chromophore with distorted oct…

Syntheses, structures, electrochemical measurements and magnetic properties of two iron(III) complexes derived from N,N′-o-phenylenebis(3-ethoxysalic…

2011

Abstract The work in this paper presents syntheses, characterizations, crystal structures, electrochemical measurements and magnetic properties of two iron(III) compounds [FeIIIL(H2O)(MeOH)](ClO4) (1) and [FeIIIL(H2O)2](NO3)·H2O (2) derived from the Schiff base compartmental ligand N,N′-o-phenylenebis(3-ethoxysalicylaldimine) (H2L). The two compounds are characterized by elemental analyses, IR, electrospray ionization mass (ESI-MS positive), UV–Vis spectra and conductance values. The structures of 1 and 2 show that these are mononuclear compounds having the metal ion in the N2O2 compartment. Two mononuclear moieties in both the compounds are self-assembled due to bifurcated hydrogen bonds i…

Phase Trapping in Multistep Spin Crossover Compound

2020

The dimeric motif is the smallest unit for two interacting spin centers allowing for systematic investigations of cooperative interactions. As spin transition compounds, dinuclear complexes are of particular interest, since they potentially reveal a two-step spin crossover (SCO), switching between the high spin-high spin [HS-HS], the high spin-low spin [HS-LS], and the low spin-low spin [LS-LS] states. Herein, we report the synthesis and characterization of six dinuclear iron(II) complexes [FeII2(μ2-L1)2](BF4)4 (C1), [FeII2(μ2-L1)2](ClO4)4 (C2), [FeII2(μ2-L1)2](F3CSO3)4 (C3), [FeII2(μ2-L2)2](BF4)4 (C4), [FeII2(μ2-L2)2](BF4)4 (C5), and [FeII2(μ2-L2)2](BF4)4 (C6), based on the 1,3,4-thiadiazo…

Long-Distance Magnetic Interaction of Exchange-Coupled Copper Dimers with Nitronyl Nitroxide and tert-Butyl Nitroxide Radicals

2009

To study long-distance magnetic interactions between exchange-coupled metal centers and coordinated radical moieties, two new homodimetallic Cu(II) complexes held together by the chelating ligand L(nPr) = N,N,N',N'-tetrakis(N-propyl-2-benzimidazolyl)-2-hydroxy-1,3-diaminopropane and additionally bridged by either a nitronyl nitroxide (NIT) or a tert-butyl nitroxide (NOA) radical-substituted benzoate have been prepared. The complexes have been investigated by X-ray crystallography, magnetic susceptibility measurements, electron paramagnetic resonance (EPR) spectroscopy, and density functional theory (DFT) calculations. For comparison additionally the related copper dimer with the bridging di…

Folded Cr12Co12 and Cr12Ni12 wheels: a sharp increase in nuclearity of heterometallic chromium rings

2014

Two novel record-sized heterometallic Cr12M12 (M = Co, Ni) chromium wheels with an unusual saddle-like architecture are created by reacting appropriate precursor complexes with the bridging ligand 2,2'-bipyrimidine.

Tuning the Basicity of Synergic Bimetallic Reagents: Switching the Regioselectivity of the Direct Dimetalation of Toluene from 2,5‐ to 3,5‐Positions

2008

Meta-meta metalation: Remarkably, toluene can be directly dimanganated or dimagnesiated at the 3,5-positions using bimetallic bases with active Me3SiCH2 ligands (see scheme, blue). In contrast, n-butyl ligands lead to 2,5-metalation (red). tmp=2,2,6,6-tetramethylpiperidide.

1,2,4-Triazole Schiff base directed synthesis of polynuclear iron complexes: Investigating the magnetic properties going from a dimer to a 1D chain t…

2018

Abstract Based on two functionalized Schiff base ligands 4-(1H-imidazol-5-ylmethylene-amino)-4H-1,2,4-triazole (imztrz) and 4-(p-tolylidene-amino)-4H-1,2,4-triazole (toltrz), a series of three triazole based polynuclear Fe complexes has been prepared. Compounds {[FeII(toltrz)2(C2O4)]·10H2O}n (1) and {[FeII(5-imztrz)(C2O4)]·2H2O}n (2) are oxalate bridged FeII complexes with 1 showing a linear 1D chain structure and 2 exhibiting a zigzag chain based 3D interpenetrating framework. Both structures show rather big voids in the 3D architecture (∼15% of the crystal volume). Compound (5-imztrzH)2[FeIII2(cit4−)2(H2O)2]·6H2O (3) is a binuclear FeIII complex bridging by two citrate ligands to form a f…

Front Cover: Filling the Gap in the Metallacrown Family: The 9‐MC‐3 Chromium Metallacrown (Chem. Eur. J. 13/2021)

2021

With Phosphinophosphonic Acids to Nanostructured, Water-Soluble, and Catalytically Active Rhodium Clusters

2007

A Vanadium(III) Complex with Blue and NIR-II Spin-Flip Luminescence in Solution.

2020

Luminescence from Earth-abundant metal ions in solution at room temperature is a very challenging objective due to the intrinsically weak ligand field splitting of first-row transition metal ions, which leads to efficient nonradiative deactivation via metal-centered states. Only a handful of 3d

Increasing the nuclearity and spin ground state in a new family of ferromagnetically-coupled {Ni10} disk-like complexes bearing exclusively end-on br…

2018

The synthesis of a new family of ferromagnetically-coupled {Ni10} clusters counterbalanced by various [Ln(NO3)5]2− ions is herein described. The resulting compounds are organic chelate-free and the metal ions are exclusively bridged by end-on azido ligands to stabilize a beautiful disk-like topology reminiscent of the structure of the brucite mineral.

Counter-complementarity control of the weak exchange interaction in a bent {Ni(ii)3 complex with a μ-phenoxide-μ-carboxylate double bridge

2019

We have prepared and structurally characterized a novel {Ni3} bent complex bearing a double μ-phenoxide-μ-carboxylate bridge. Both terminal Ni(ii) sites are symmetry related, offering a simplified exchange interaction scheme. DC magnetic data is consistent with a weak antiferromagnetic interaction between the central and terminal Ni(ii) ions. As expected for a Ni(ii) system, local zero-field splitting is observed, which can be experimentally established. Broken symmetry quantum chemical calculations, as well as ab initio CASSCF-SA-SOC computations that support the magnetic experimental data, were also performed. From the analysis of other reported closely related Ni(ii) systems, a counter-c…

A novel Cu(II) dimer containing oxime-hydrazone Schiff base ligands with an unusual mode of coordination: Study of magnetic, autoreduction and soluti…

2013

Abstract Synthesis of a new hydrazone based Schiff base ligand, 3-methylpyrazole-5-carbohydrazone of 2,3-butanedione monoxime (HL) is reported. The reaction of Cu(ClO4)2·6H2O with HL in any ratio in ethanol affords the dinuclear complex [CuL(EtOH)]2(ClO4)2·2H2O (1). An unusual coordination mode of the ligand was observed, in which the ligand forms stable six and five membered chelate rings around the metal centres without enolization of the carbonyl group of the hydrazone moiety. The same coordination behavior of the ligand was observed in its cobalt(III) complex. The reaction of CoCl2·6H2O in methanol with the ligand HL affords the mononuclear complex [CoL2]Cl (2). Both 1 and 2 were charac…

Structural characterization and magnetic property studies of a mixed-valence {CoIIICoII4} complex with a μ4-oxo tetrahedral {CoII4} motif

2020

We have synthesized and structurally characterized a new mixed valence pentanuclear Co complex, bearing a rare μ4-O-tetrahedral CoII4 unit, by employing a pyridine-like Schiff base ligand. We have performed DC magnetic susceptibility and magnetization measurements over polycrystalline samples and chemical quantum computations in order to understand the exchange interaction pattern within Co(II) sites and ground state magnetic anisotropy. This new complex shows an overall antiferromagnetic exchange interaction whose strength strongly depends on the local symmetry of Co(II) sites. Also, local ion magnetic anisotropy reveals a strongly axial behaviour with the lowest Kramers doublet (KD) at ea…

2-Amino-2-methyl-1,3-propanediol (ampdH2) as ligand backbone for the synthesis of cobalt complexes: Mononuclear Co(II), binuclear Co(II,III) and hexa…

2013

Abstract Three cobalt complexes have been synthesized using 2-amino-2-methyl-1,3-propanediol (ampdH2) and its Schiff base derivative ligands and structurally characterized. The three complexes 1, 2 and 3 are very different and consist of mononuclear Co(II), mixed-valence binuclear Co(II,III) and mixed-valence hexanuclear Co(II,III) complexes respectively. The properties of the coordinated donor atoms of the ligand play the predominant role in stabilizing the oxidation states of the cobalt centers. The presence of intermolecular hydrogen bonds in 1 via non-coordinating perchlorate ions lead to the formation of a 1D-Chain network while a sheet-like 2D network was observed in 3.

Magnetism of metallacrown single-molecule magnets: From a simplest model to realistic systems

2018

Electronic and magnetic properties of molecular nanomagnets are determined by competing energy scales due to the crystal field splitting, the exchange interactions between transition metal atoms, and relativistic effects. We present a comprehensive theory embracing all these phenomena based on first-principles calculations. In order to achieve this goal, we start from the ${\mathrm{FeNi}}_{4}$ cluster as a paradigm. The system can be accurately described on the ab initio level yielding all expected electronic states in a range of multiplicities from 1 to 9, with a ferromagnetic ground state. By adding the spin-orbit coupling between them we obtain the zero-field splitting. This allows to in…

Magnetism and variable temperature and pressure crystal structures of a linear oligonuclear cobalt bis-semiquinonate

2016

The crystal structure of the first oligomeric cobalt dioxolene complex, Co3(3,5-DBSQ)2((t)BuCOO)4(NEt3)2, 1, where DBSQ is 3,5-di-tert-butyl-semiquinonate, has been studied at various temperatures between 20 and 200 K. Despite cobalt-dioxolene complexes being generally known for their extensive ability to exhibit valence tautomerism (VT), we show here that the molecular geometry of compound 1 is essentially unchanged over the full temperature range, indicating the complete absence of electron transfer between ligand and metal. Magnetic susceptibility measurements clearly support the lack of VT between 8 and 300 K. The crystal structure is also determined at elevated pressures in the range f…

Mit Phosphanylphosphonsäuren zu nanostrukturierten, wasserlöslichen und katalytisch aktiven Rhodiumclustern

2007

Solvent-induced high-spin transition in double-decker 3d–4f metallacrowns

2019

Element-specific magnetic spin and orbital magnetic moments of $3d\text{\ensuremath{-}}4f$ double-decker metallacrown molecules have been investigated using x-ray magnetic circular dichroism. The double-decker metallacrowns comprise one rare-earth Gd(III) or Tb(III) ion embedded between two squared scaffolds of four Ni(II) ions. We observe a strong increase of the Ni(II) moments if the molecules are dissolved in methanol, indicating a spin crossover from a low-spin to a high-spin state. In contrast, dichloromethane does not change the spin state. This result is explained by a change of the coordination environment of nickel. The comparison of charge-transfer multiplet calculations with the …

Spin Crossover and Long-Lived Excited States in a Reduced Molecular Ruby.

2020

Abstract The chromium(III) complex [CrIII(ddpd)2]3+ (molecular ruby; ddpd=N,N′‐dimethyl‐N,N′‐dipyridine‐2‐yl‐pyridine‐2,6‐diamine) is reduced to the genuine chromium(II) complex [CrII(ddpd)2]2+ with d4 electron configuration. This reduced molecular ruby represents one of the very few chromium(II) complexes showing spin crossover (SCO). The reversible SCO is gradual with T 1/2 around room temperature. The low‐spin and high‐spin chromium(II) isomers exhibit distinct spectroscopic and structural properties (UV/Vis/NIR, IR, EPR spectroscopies, single‐crystal XRD). Excitation of [CrII(ddpd)2]2+ with UV light at 20 and 290 K generates electronically excited states with microsecond lifetimes. This…

Synthesis and antimicrobial screening of tetra Schiff bases of 1,2,4,5-tetra (5-amino-1,3,4-thiadiazole-2-yl)benzene

2014

Abstract In the present study, novel tetra Schiff bases were synthesized by condensation of 1,2,4,5-tetra (5-amino-1,3,4-thiadiazole-2-yl)benzene with different aromatic aldehydes. The chemical structures were confirmed by means of IR, 1 H NMR, 13 C NMR, and elemental analysis. All compounds were screened for antibacterial ( Staphylococcus aureus ATCC-9144, Staphylococcus epidermidis ATCC-155, Micrococcus luteus ATCC-4698, Bacillus cereus ATCC-11778, Escherichia coli ATCC-25922, and Pseudomonas aeruginosa ATCC-2853) and antifungal ( Aspergillus niger ATCC-9029 and Aspergillus fumigatus ATCC-46645) activities by paper disc diffusion technique. The minimum inhibitory concentrations (MICs) of …

Strongly Red-Emissive Molecular Ruby [Cr(bpmp)2]3+ Surpasses [Ru(bpy)3]2+

2021

Gaining chemical control over the thermodynamics and kinetics of photoexcited states is paramount to an efficient and sustainable utilization of photoactive transition metal complexes in a plethora of technologies. In contrast to energies of charge transfer states described by spatially separated orbitals, the energies of spin-flip states cannot straightforwardly be predicted as Pauli repulsion and the nephelauxetic effect play key roles. Guided by multireference quantum chemical calculations, we report a novel highly luminescent spin-flip emitter with a quantum chemically predicted blue-shifted luminescence. The spin-flip emission band of the chromium complex [Cr(bpmp)2]3+ (bpmp = 2,6-bis(…

A Click‐Functionalized Single‐Molecule Magnet Based on Cobalt(II) and Its Analogous Manganese(II) and Zinc(II) Compounds

2014

A mononuclear CoII single-molecule magnet suitable for click chemistry was investigated. [M(oda)(aterpy)] complexes (oda2– = oxodiacetate, aterpy = 4′-azido-2,2′:6′,2″-terpyridine) with M = MnII, ZnII, and CoII were synthesized as azide-functionalized building blocks for the copper-catalyzed azide–alkyne cycloaddition reaction. The required structural integrity of the complexes in solution was proven in great detail by using ESI-MS and NMR spectroscopy. For the six-coordinate [Co(oda)(aterpy)] complex, single-molecule magnet behavior was confirmed with an effective energy barrier of 4.2 cm–1.

The First 1,3,4‐Oxadiazole Based Dinuclear Iron(II) Complexes Showing Spin Crossover Behavior with Hysteresis

2015

Three new dinuclear complexes [FeII2(μ-L)2]X4 (L is the bis-tridentate ligand 2,5-bis{[(2-pyridylmethyl)amino]methyl}-1,3,4-oxadiazole and X = ClO4–, BF4– and CF3SO3–) have been synthesized and fully characterized by single-crystal X-ray diffraction, Mossbauer spectroscopy and magnetic susceptibility measurements. Upon cooling, a trapped [high-spin–low-spin] state of the iron(II) centres is detected. Depending on the counterion, a pronounced thermal hysteresis is found. In one case, it was possible to observe a space group change that accompanies the spin transition. This is the first system showing spin crossover based on an oxadiazole ligand.

Slow relaxation of magnetization in a {Fe6Dy} complex deriving from a family of highly symmetric metallacryptands

2019

The synthesis and characterization of a new family of isostructural {Fe6Ln} complexes, (pipH)3{Fe6Ln(shiH)3(shi)6}·1.5 pip·xH2O (Ln = Gd (1), Dy (2), Tb (3) and Y (4), pip = piperidine, and shi3− = salicylhydroxamic acid) is reported. The resulting compounds possess an exceptionally unique structure of a metallacrown-like motif while the overall complexes feature more the structure of metallacryptates. Magnetic studies are reported and reveal that the {Fe6Dy} analogue belongs to the single-molecule magnet (SMM) family.

12-MC-4 metallacrowns as versatile tools for SMM research

2015

Abstract The outstanding chemical and structural features of 12-MC-4 metallacrowns allow for versatile applications in magneto-chemical research. Herein, we present three novel approaches. The heterometallic, or magnetic director approach, provides a targeted way to attain unusual high-spin ground states in 12-MC-4 complexes. Further, the first cobalt metallacrowns of salicylhydroxamic acid have been established. They comprise a diamagnetic scaffold which facilitates an engineering of the magnetism of the central guest ion and thus three novel SMMs based on single Co(II) ions have been established. Finally, click chemistry has been utilized to realize a linkage of an azide-functionalized mo…

Exchange coupling across the cyanide bridge: structural and DFT interpretation of the magnetic properties of a binuclear chromium(III) complex.

2006

The reaction of [Cr(CN)6]3− with a mixture of trans-[Cr(cyclam)(OH)2]Cl, [Cr(cyclam)(OH)Cl]Cl and [Cr(cyclam)Cl2]Cl affords the cyanide bridged dimer, trans-[HO–Cr(cyclam)–NC–Cr(CN)5]−. The tetraphenylphosphonium salt of the anion crystallizes in space group P21/n and shows a bent arrangement of the Cr1–CN–Cr2 unit with the Cr1–CN bond angle at 166.9° and CN–Cr2 at 160.32°. The Cr2–O bond, trans to the hexacyanide fragment, is very short at 1.902 A. Two dimers are held together by two hydrogen bonds connecting the Cr2–OH group of each dimer with one of the NH groups of the cyclam ligand of an adjacent molecule, leading to an almost linear configuration. These dimers of dimers get packed par…

Assessing the reactivity of sodium alkyl-magnesiates towards quinoxaline : single electron transfer (SET) vs. nucleophilic alkylation processes

2015

By exploring the reactivity of sodium butyl-magnesiate (1) supported by the bulky chelating silyl(bisamido) ligand {Ph2Si(NAr*)2}(2-) (Ar* = 2,6-iPr2-C6H3) towards Quinoxaline (Qx), the ability of this bimetallic system to effectively promote SET processes has been disclosed. Thus 1 executes the single-electron reduction of Qx affording complex (2) whose structure in the solid state contains two quinaxolyl radical anions Qx˙ stabilised within a dimeric magnesiate framework. Combining multinuclear NMR and EPR measurements with DFT calculations, new insights into the constitution of 2 in solution and its magnetic behaviour have been gained. Further evidence on the SET reactivity of 1 was foun…

A Discrete μ 4 ‐Oxido Tetranuclear Iron(III) Cluster

2012

Reaction of a Schiff base ligand derived from salicyloyl hydrazide and diacetyl monooxime (H2L) with a triangular μ3-oxido-centered [Fe3(μ3-O)]7+ core yields a new tetranuclear iron(III) complex. FeIII4(μ4-O) crystallizes in the triclinic space group P. Structural studies reveal that this tetranuclear iron(III) complex is a new structure type of an uncharged (alkoxido)(oxido)iron(III) cluster in which the four iron(III) ions are located at the corners of a distorted tetrahedron. A study of the magnetic properties supports the presence of antiferromagnetic interactions through the central μ4-oxido ion as well as the μ2-methoxy groups present, giving an an S = 0 ground state. Mossbauer spectr…

Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex

2019

Abstract Photoactive metal complexes employing Earth‐abundant metal ions are a key to sustainable photophysical and photochemical applications. We exploit the effects of an inversion center and ligand non‐innocence to tune the luminescence and photochemistry of the excited state of the [CrN6] chromophore [Cr(tpe)2]3+ with close to octahedral symmetry (tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). [Cr(tpe)2]3+ exhibits the longest luminescence lifetime (τ=4500 μs) reported up to date for a molecular polypyridyl chromium(III) complex together with a very high luminescence quantum yield of Φ=8.2 % at room temperature in fluid solution. Furthermore, the tpe ligands in [Cr(tpe)2]3+ are redox non‐innocent, …

A Co36Cluster Assembled from the Reaction of Cobalt Pivalate with 2,3-Dicarboxypyrazine

2009

A record Co36 cluster is prepared. This mixed-valent compound containing CoII and CoIII centers is formed in the reaction of a dinuclear cobalt pivalate species with the polydentate 2,3-dicarboxypyrazine ligand. In terms of magnetic properties it behaves as a {Co16-Co16} supramolecular dimer in which the S = A spin ground states of each monomer do not interact. Fil: Alborés, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, M…

Ferromagnetic coupled μ-phenoxo-μ-carboxylato heterodinuclear complexes based on the Cr(salen) moiety: Structural and magnetic characterization

2009

The synthesis, crystal structure, and magneto-chemical characterization of two new unprecedented μ-phenoxo-μ-carboxylato heterodinuclear complexes based on the Cr(salen) moiety (salen = N,N′-bis(salicylidene)ethylenediamine), [MII(O2C(CH3)3)(OH2)2(μ-O2C(CH3)3)(μ-salen)CrIII(O2C(CH3)3)], M = Ni (2), Co(3) are reported. The dinuclear complexes were obtained starting from the mononuclear trans-[Cr(salen)(CN)2]PPh4 (1), whose crystal structure is also reported. They show a trans arrangement of the Cr(salen) unit, bridging through the phenolate O atoms to a second metal center. An additional μ2-O2-carboxylato bridge and a further monodentating carboxylate ligand complete the roughly octahedral C…

Structural and magnetic investigations of the mixed-valence Fe(II,III) two-dimensional layer complex, [Fe2(II) Fe2(III)(HCOO)10(C6H7N)6]n.

2004

The structure of the complex, [Fe2(II)Fe2(III)(HCOO)10(C6H7N6)n, (1) exhibits a neutral two-dimensional layer network of alternating iron(II) and iron(III) ions, bridged equatorially by formate groups. All iron atoms are octahedrally coordinated, with iron(III) coordinating axially to one gamma-picoline and one formate group, while the iron(II) centers interact axially with two gamma-picoline groups, above and below the layer plane. The complex crystallizes in the triclinic space group P1 at all studied temperatures [at 120 K, the cell dimensions are: a = 10.228(1), b = 12.071(1), c = 12.072(1) A, alpha = 89.801(2), beta = 71.149(2), gamma = 73.371(2) degrees]. An intralayer antiferromagnet…

High-frequency EPR study on Cu4Cu- and Co4Co-metallacrown complexes

2019

Abstract High-frequency/high-field electron paramagnetic resonance studies on two homonuclear 12-MC-4 metallacrown complexes Cu4Cu and Co4Co are presented. For Cu4Cu, our data imply axial-type g-anisotropy with g x = 2.03 ± 0.01 , g y = 2.04 ± 0.01 , and g z = 2.23 ± 0.01 , yielding g = 2.10 ± 0.02 . No significant zero field splitting (ZFS) of the ground state mode is observed. In Co4Co, we find a m S = ± 3 / 2 ground state with g = 2.66 . The data suggest large anisotropy D of negative sign.

A New Co-Ni-Heterometallic Butterfly Complex Obtained via a Novel Synthesis Approach

2011

Abstract. The heterometallic complex [Co2Ni2(OH)2(O2CtBu)6(HOEt)6]·2EtOH (1) with a so called butterfly structural motif was prepared by reaction of the homometallic precursor complexes [Co2(H2O)(O2CtBu)4(HO2CtBu)4] and [Ni2(H2O)(O2CtBu)4(HO2CtBu)4] in an one to one ratio under elevate temperature. Complex 1 was characterized by single-crystal X-ray diffraction, atomic absorption spectroscopy, elemental analyses, IR spectroscopy, and mass spectrometry. The magnetic data show an overall antiferromagnetic behavior, which can be explained with three different coupling constants, resulting in a paramagnetic ground state.

Aggregation of [Ln(12)(III)] clusters by the dianion of 3-formylsalicylic acid. Synthesis, crystal structures, magnetic and luminescence properties

2019

Three isostrucutral dodecanuclear clusters with the general formula [Ln(12)(fsa)(12)(mu f(3)-OH)(12)(DMF)(12)]center dot nDMF (fsa(2-) is the dianion of 3-formylsalicylic acid; Ln = Eu 1, Gd 2, Dy 3) have been obtained from the reaction of fromylsalicyclic acid (H(2)fsa), tetrabutylammonium hydroxide and Ln(NO3)(3)center dot 6H(2)O in methanol/DMF. Their structure consists of four vertex-sharing heterocubanes. Each heterocubane unit is assembled from four Ln(III) ions, three mu(3)-OH groups and one mu(3)-oxygen atom arising from the fsa(2-) carboxylato group. The photophysical properties of the europium derivative investigated at both 300 and 80 K sustain a relative intense emission obtaine…

Azine-bridged octanuclear copper(II) complexes assembled with a one-stranded ditopic thiocarbohydrazone ligand.

2005

Combination of single-molecule magnet behaviour and luminescence properties in a new series of lanthanide complexes with tris(pyrazolyl)borate and ol…

2020

A series of tris(pyrazolyl)borate mono-, di- and trinuclear complexes, [Tp2Ln]nX (Ln = Eu, Tb, Gd, Dy, Xn− = various mono-, bis- and tris(β-diketonates) has been prepared. The Tb3+ and Dy3+ complexes are luminescent single molecular magnets (SMM) and exhibit luminescence quantum efficiencies up to 73% for the Tb3+ and 4.4% for the Dy3+ compounds. Similar Eu3+ complexes display bright emission only at lower temperatures. The Dy3+ and Tb3+ complexes possess SMM behavior in a non-zero dc field at low temperatures, while the polynuclear Dy3+ complexes also show slow magnetic relaxation even in zero dc field up to 8 K. Ueff-values determined from dynamic magnetic measurements were up to 31 and 6…

Structural and magnetic characterization of a 1D chain of [Co(II)2(mu-aqua)(mu-carboxylate)2] strung cores.

2009

A novel 1D chain built up from stringing of [Co2(μ-OH 2)(μ-O2CC(CH3)3)2] units with the bridging 2,2′-bipyrimidine ligand has been synthesized and structurally characterized. The chains are well isolated from each other by the bulky tert-butyl groups of the carboxlyates and show an alternating zigzag configuration for the Co(II) metallic centres. DC magnetic measurements show anti-ferromagnetic coupling, Jca.-3 cm-1 between adjacent Co(II) ions along the chain. Noticeably, good data fitting was obtained by means of simple models that neglect any kind of first order orbital contribution to the spin ground state, which is normally observed in Co(II) complexes. These results were further confi…

Tailoring the Exchange Interaction in Covalently Linked Basic Carboxylate Clusters through Bridging Ligand Selection

2012

We are reporting new dimeric units of basic carboxylates bearing the {Fe III 2M IIO} motif for M = Co and Ni, covalently bound through the tetradentate bridging (LL) 2,2′-azopyiridine (azpy) and 2,3-di(2-pyridyl)quinoxaline ligands (dpq). We structurally characterized the hexanuclear clusters, and their magnetic properties have been fully analyzed. DFT calculations have been performed as a supplementary tool. All results evidence a weak antiferromagnetic interaction through the bridging ligands between isolated spin ground states arising from intra-Fe 2MO core exchange couplings. Together with the pioneer 2,2′-bipyrimidine bridged systems, the new complexes reported constitute a family of c…

Vibrational properties of 1D- and 3D polynuclear spin crossover Fe(II) urea-triazoles polymer chains and quantification of intrachain cooperativity

2020

Abstract The vibrational dynamics of the iron centres in 1D and 3D spin crossover Fe(II) 4-alkyl-urea triazole chains have been investigated by synchrotron based nuclear inelastic scattering. For the 1D system, the partial density of phonon states has been modelled with density functional theory methods. Furthermore, spin dependent iron ligand distances and vibrational modes were obtained. The previously introduced intramolecular cooperativity parameter H coop (Rackwitz et al, Phys. Chem. Chem. Phys. 2013, 15, 15450) has been determined to −31 kJ mol−1 for [Fe(n-Prtrzu)3(tosylate)2] and to +27 kJ mol−1 for [Fe(n-Prtrzu)3(BF4)2]. The change of sign in H coop is in line with the incomplete an…

Beyond the Heisenberg Model: Anisotropic Exchange Interaction between a Cu-Tetraazaporphyrin Monolayer andFe3O4(100)

2013

The exchange coupling of a single spin localized at the central ion of Cu-tetraazaporphyrin on a magnetite(100) surface has been studied using x-ray magnetic circular dichroism (XMCD). Sum rule analysis of the XMCD spectra results in Cu spin and orbital magnetic moments as a function of the applied external field at low temperatures (20 K). The exchange coupling is positive for magnetization direction perpendicular to the surface (ferromagnetic) while it is negative for in-plane magnetization direction (antiferromagnetic). We attribute the anisotropy of the Heisenberg exchange coupling to an orbitally dependent exchange Hamiltonian.

Exploring the exchange interaction in a mixed valence {CoII4CoIII2} hexanuclear cluster with novel topology

2012

Abstract Reaction between [Co2(μ-OH2)(μ-Piv)2(Piv)2(HPiv)4] and a (salicylidene)ethanolamine ligand under ambient reaction conditions, affords hexanuclear complexes [CoIII2CoII4(Piv)8(HPiv)2(L)2(OH)2] (1–2). Both products have been characterized crystallographically and found to be mixed-valent, containing divalent and trivalent Co centers. Down to 30 K, the variable-temperature magnetic susceptibility data are dominated by the single-ion properties of high spin Co(II) centers with distorted-octahedral coordination geometries. Below this temperature, the effect of intramolecular ferromagnetic exchange interactions becomes apparent. Magnetic data has been analyzed in terms of ground isolated…

A Series of MIICuII3 Stars (M = Mn, Ni, Cu, Zn) Exhibiting Unusual Magnetic Properties

2014

The work in this report describes the syntheses, electrospray ionization mass spectromtery, structures, and experimental and density functional theoretical (DFT) magnetic properties of four tetrametallic stars of composition [M(II)(Cu(II)L)3](ClO4)2 (1, M = Mn; 2, M = Ni; 3, M = Cu; 4, M = Zn) derived from a single-compartment Schiff base ligand, N,N'-bis(salicylidene)-1,4-butanediamine (H2L), which is the [2 + 1] condensation product of salicylaldehyde and 1,4-diaminobutane. The central metal ion (Mn(II), Ni(II), Cu(II), or Zn(II)) is linked with two μ2-phenoxo bridges of each of the three [Cu(II)L] moieties, and thus the central metal ion is encapsulated in between three [Cu(II)L] units. …

Rational linkage of magnetic molecules using click chemistry

2015

Established CuAAC click reactions are used for the first time to assemble magnetic molecules to an extended molecular arrangement. This novel synthetic approach is expected to be a general approach to link SMMs as an important precondition to realize quantum computing.

Fully interlocked three-dimensional molecular scaffolding: Synthesis, X-ray structure, magnetic and nitrogen sorption study

2012

Abstract The reaction of M(NO3)2·6H2O (M = Co or Ni), N,N-diethyl-ethylenediamine (deen) and sodium dicyanamide (dca) afforded the complex {[M(deen)(μ1,5-dca)2]}n (where for 1, M = Co and for 2, M = Ni). The complexes have been characterized structurally and magnetically. X-ray analysis reveals that the isomorphous complexes 1 and 2 feature similar infinite three-dimensional scaffolding-like structure to generate the fascinating molecular assembly. All the {N(CN)2}− ligands present in the complexes are connected to the symmetry related metal centers in an end-to-end fashion through bent {N(CN)2}− ligands. The zigzag linkage propagates parallel to three crystallographic axes to form a fully …

Tri- and tetranuclear heteropivalate complexes with core {Fe2Ni O} (x = 1, 2): Synthesis, structure, magnetic and thermal properties

2019

Abstract The reactions of complex [Fe2Ni(O)(Piv)6(Et2O)(H2O)2] (1) with 1,10-phenanthroline (phen) and 2,2′-bipyridine (bpy) gave the following new coordination compounds: the trinuclear complex [Fe2Ni(O)(Piv)6(phen)H2O]·(C2H5)2O (2), the tetranuclear ones [Fe2Ni2(OH)2(Piv)8(phen)2] (3) and [Fe2Ni2(OH)2(Piv)8(bpy)2] (4), depending on the crystallization conditions. According to single crystal X-ray diffraction data, all the compounds have molecular structures. The Mossbauer spectra of 1–3 correspond to high-spin Fe3+ ions in an octahedral environment consisting of oxygen atoms. The DC magnetic susceptibility studies and quantum-chemical analysis of intra- and intermolecular J pathways using…

Spontaneous Resolution of a Triple‐Stranded Dinickel(II) Helicate Generated via Intermolecular Transamination Reaction of S ‐Methylisothiocarbohydraz…

2008

The reaction of S-methylisothiocarbohydrazide hydroiodide [H2NNHC(SCH3)NNH2·HI] with NiCl2·6H2O in water at room temperature yielded a triple-stranded dinickel(II) helicate [NiII(L1–L1)3NiII]I4·4H2O (14+·4I–·4H2O), where L1–L1 = H2NNHC(SCH3)NNC(SCH3)NHNH2, in 35 % yield, which spontaneously separates in enantiomers upon crystallization. The enantiomers do not racemize at room temperature, even not after 15 h of heating at 90 °C. X-ray diffraction structures of both enantiomers, chiroptical and magnetic properties of 14+·4I–·4H2O are reported. Demetallation of the complex by treatment with S2– resulted in 3,6-bis(methylthio)-1,4-dihydro-1,2,4,5-tetrazine (2). Compound 2 undergoes 2-e– oxidat…

Structures and Magnetic Properties of Bis(μ‐phenoxido), Bis(μ‐phenoxido)‐μ‐carboxylato and Bis(μ‐phenoxido)bis(μ‐carboxylato) Fe III Ni II Compounds …

2015

This report describes the syntheses, characterization, crystal structures and magnetic properties of five dinuclear FeIIINiII compounds derived from two Robson-type tetraiminodiphenol macrocyclic ligands H2L1 and H2L2, which are the [2+2] condensation products of 4-ethyl-2,6-diformylphenol and 1,3-diaminopropane (for H2L1) or 2,2-dimethyl-1,3-diaminopropane (for H2L2). The compositions of the compounds are [FeIII(N3)2L1NiII(H2O)2](ClO4) (1), [FeIII(benzoato)L1NiII(H2O)(μ1,3-benzoato)](ClO4) (2), [FeIII(benzoato)L2NiII(H2O)(μ1,3-benzoato)](ClO4) (3), [FeIIIL2NiII(μ1,3-acetato)2](ClO4)·H2O (4) and [FeIIIL2NiII(μ1,3-propionato)2](ClO4)·H2O (5). The bridging moieties between the two metal ions …

Limiting nuclearity in formation of polynuclear metal complexes through [2 + 3] cycloaddition: synthesis and magnetic properties of tri- and pentanuc…

2014

A tridentate ligand p-chloro-2-{(2-(dimethylamino)ethylimino)methyl}phenol (HL) was used to generate an octahedral nickel complex [Ni(L)Cl(H2O)2] 1 which was further converted into a square-planar nickel complex [Ni(L)(N3)] 2. The [2 + 3] cycloaddition reaction between metal coordinated azide 2 and different organonitriles under microwave irradiation afforded tri- and pentanuclear nickel(II) complexes 4a-4c. Reaction with benzonitrile and 3-cyano pyridine furnished the trinuclear species [Ni3L2(5-phenyltetrazolato)4(DMF)2] 4a and [Ni3L2{5-(3-pyridyl)-tetrazolato}4(DMF)2]·2H2O 4b, respectively. The nickel centers were found to be linearly disposed to each other and the complex is formed by a…

Syntheses, characterisation, magnetism and photoluminescence of a homodinuclear Ln(III)-Schiff base family.

2009

A novel family of homodinuclear complexes of the general formula [Ln(2)L(2)(X)(2)] (where Ln = Nd(3+), Pr(3+), Sm(3+) and Tb(3+) for 1, 2, 3 and 4, respectively and X, the coordinated NO(3)(-) or Cl(-) anion) has been synthesised from the corresponding lanthanide(III) salts with the pentadentate dianionic Schiff base ligand, H(2)L [N(1),N(3)-bis(salicylideneimino)diethylenetriamine], that exhibits a N(3)O(2) donor set. Single crystal X-ray diffraction studies evidenced the isostructurality of this family of centrosymmetric neutral dinuclear entities where the Ln(III) metal centres are coupled together by two phenolato oxygen atoms belonging to two units of ligand (H(2)L). Interestingly, the…

Studies of a molecular hourglass: synthesis and magnetic characterisation of a cyclic dodecanuclear {Cr10Cu2} complex.

2006

The synthesis, structure, EPR, and magnetic studies of two dodecanuclear heterometallic cyclic clusters are reported. The compounds have the general formula [R(2)NH(2)](2)[Cr(10)Cu(2)F(14)(O(2)CCMe(3))(22)] (R=Me, 1 or iPr, 2). Both structures contain an array of metal centers which describe an approximate "hourglass", with an ammonium cation in the center of each half of the figure. The chromium sites are all six-coordinate, with the two copper sites five-coordinate. The majority of metal-metal edges are bridged by a single fluoride and two pivalate ligands, while two Cr--Cu edges are bridged by a single fluoride and a single pivalate. Magnetic studies show that 1 and 2 exhibit similar (bu…

Synthesis, X-ray crystal structure and magnetic study of the 1D {[Cu(N,N-diethyl-1,2-ethanediamine)(μ1,5-dca)(dca)]}n complex

2007

Abstract A new complex, {[CuL(μ1,5-dca)(dca)]}n (1), has been synthesized from the reaction of Cu(NO3)2 · 3H2O, N,N-diethyl-1,2-ethanediamine (L) and sodium dicyanamide (Nadca) in aqueous medium. Single crystal X-ray analysis reveals that the complex has a 1D infinite zigzag chain structure in which copper(II) ions are bridged by single dicyanamide ligands in an end-to-end fashion. The chains propagate parallel to the crystallographic b-axis and they are stacked one upon another along the c-axis. The coordination environment of the copper(II) centers are distorted square-pyramidal. Of the four coordination sites of the basal plane of the square-pyramid, two are occupied by the nitrogen atom…

Magnetic Molecular Rectangles Constructed from Functionalized Nitronyl‐Nitroxide Ligands and Lanthanide(III) Ions

2020

A family of heterometallic wheels containing potentially fourteen hundred siblings

2005

The synthesis and structure of new heterometallic wheels are reported, with preliminary studies of selected compounds.

Analyzing the enforcement of a high-spin ground state for a metallacrown single-molecule magnet

2016

We have studied element-selective magnetic properties of the hetero- and homometallic metallacrowns $\mathrm{Cu}{(\mathrm{II})}_{2}[12\ensuremath{-}{\mathrm{MC}}_{YN(Shi)}\ensuremath{-}4]$ ($Y=\text{Cu}$, Fe, in short ${\mathrm{CuCu}}_{4}$ and ${\mathrm{CuFe}}_{4}$). These metallacrowns comprise four Fe or Cu ions surrounding a central Cu ion. Using x-ray magnetic circular dichroism we have probed local symmetries, electronic configuration, orbital and spin magnetic moments of the magnetic ions. The ratio between the Cu and Fe moment of $\ensuremath{-}0.11$ is independent of temperature in the range of 15 K to 90 K. The Cu moment shows antiparallel to the Fe moment. For ${\mathrm{CuCu}}_{4}…

Single Molecule Magnet Features in the Butterfly [Co III 2 Ln III 2 ] Pivalate Family with Alcohol‐Amine Ligands

2021

Structural and Magnetic Characterization of a μ-1,5-Dicyanamide-Bridged Iron Basic Carboxylate [Fe3O(O2C(CH3)3)6] 1D Chain

2008

We are reporting an unprecedented example of a mu-1,5-dicyanamide (dca)-bridged iron basic carboxylate, [Fe3O(O2C(CH3)3)6], 1D chain. As revealed from X-ray determination, the Fe3O cores are arranged in a zigzag configuration along the chain and strictly aligned in the same plane. The chains are well-isolated by the bulky tert-butyl groups. Magnetic measurements showed that the Fe3O units are weakly antiferromagnetically coupled (J = -0.6 cm(-1)) through the dca ligand while possessing a well-isolated S = 1/2 spin ground state arising from competing antiferromagnetic interactions.

Modeling the Geometric, Electronic, and Redox Properties of Iron(III)-Containing Amphiphiles with Asymmetric [NN′O] Headgroups

2011

Two iron(III)-containing amphiphiles 1 and 2 have been synthesized with the [NN'O] ligands HL(tBu-ODA) (2-((octadecyl(pyridin-2-ylmethyl)amino)methyl)-4,6-di-tert-butylphenol) and HL(I-ODA) (2-((octadecyl(pyridin-2-ylmethyl)amino)methyl)-4,6-diiodophenol), respectively. Compound 1 is monometallic, whereas EXAFS data suggest that 2 is a mixture of mono- and bimetallic species. The archetypical [Fe(III)(L(NN'O))(2)](+) complexes 3-9 have been isolated and characterized in order to understand the geometric, electronic, and redox properties of the amphiphiles. Preference for a monometallic or bimetallic nuclearity is dependent on (i) the nature of the solvent used for synthesis and (ii) the typ…

Ein Cobaltcluster aus der Reaktion von Cobaltpivalat mit 2,3-Dicarboxypyrazin

2009

Field-Induced Slow Magnetic Relaxation In the First Dy(III)-centered 12-Metallacrown-4 Double-Decker

2019

The reaction of Dy(O2CMe)3·xH2O and Ga(NO3)3·xH2O led to the isolation of (nBu4N)[GaIII8DyIII(OH)4(shi)8] (1). The compound possesses a unique chemical structure enclosing the central magnetic DyIII ion between diamagnetic GaIII-based metallacrown 12-MC-4 ligands. The double-decker complex exhibits field-induced single-molecule magnet (SMM) behaviour with an effective energy barrier (Ueff) of 39 K (27.1 cm−1). Consistent with the observed slow relaxation of magnetization, theoretical calculations suggest a ground state mainly determined by |±11/2> in the easy axis direction.

Organic chelate-free and azido-rich metal clusters and coordination polymers from the use of Me3SiN3: a new synthetic route to complexes with beautif…

2019

In this Feature Article, we highlight the feasibility of a new, recently developed approach towards the synthesis of high-spin molecules and single-molecule magnets (SMMs). The key to the preparation of such molecular compounds is the organic azide precursor Me3SiN3, which fosters the formation of 3d-metal azido clusters and coordination polymers without requiring the assistance of any organic chelating/bridging group. All the isolated compounds contain metallic cores which are surrounded by end-on bridging N3− groups. Consequently, the reported molecular materials exhibit ferromagnetic exchange interactions between the spin carriers, resulting in the stabilization of the maximum possible s…

Magnetic polyorganosiloxane core–shell nanoparticles: Synthesis, characterization and magnetic fractionation

2010

Abstact Here, we present the synthesis, characterization and magnetic separation of magnetic polyorganosiloxane nanoparticles. Magnetic iron oxide nanoparticles with average particle radii of 3.2 nm had been synthesized by a simple coprecipitation process of iron(II) and iron(III) salt in basic solution. Afterwards, the particles were successfully incorporated into a polyorganosiloxane network via a polycondensation reaction of trimethoxymethylsilane (T), diethoxydimethylsilane (D) and the functional monomer (chloromethylphenyl)trimethoxysilane (ClBz-T) in aqueous dispersion. A core–shell system was chosen to increase the flexibility of the system concerning size, composition and functional…

The interplay of crystallization kinetics and morphology during the formation of SnO2 nanorods: snapshots of the crystallization from fast microwave …

2011

A microwave-assisted reaction pathway to rutile SnO2nanorods was investigated. The microwave-treatment significantly reduces the reaction time compared to standard hydro-/solvothermal techniques. By moving the overall process into a shorter time slot, the growth and crystal formation during the reaction could be monitored via snapshots by trapping the intermediates through quenching. To gain a better insight into the template-free growth of one-dimensional (1D) nanostructures, a parameter-dependent (various temperatures/pressures and times were investigated) study was carried out. For all materials, the phase purity and crystallite sizes were determined by X-ray powder diffraction (XRD). Th…

Syntheses, crystal structures and magnetic properties of a series of μ-phenoxo-μ1,1-carboxylato-μ1,3-carboxylato trinickel(II) compounds.

2014

The work in this report describes the syntheses, characterization, crystal structures and magnetic properties of eight linear trinickel(ii) compounds of the composition [Ni(II)3(L(sal-pyr))2(propionate)4] (), [Ni(II)3(L(sal-pyr))2(benzoate)4]·CH3CN (), [Ni(II)3(L(sal-pip))2(acetate)4]·2CH3CN (), [Ni(II)3(L(sal-pip))2(propionate)4] (), [Ni(II)3(L(sal-pip))2(benzoate)4]·CH2Cl2 (), [Ni(II)3(L(sal-mor))2(propionate)4] (), [Ni(II)3(L(sal-mor))2(benzoate)4]·3CH2Cl2 () and [Ni(II)3(L(sal-mor))2(o-Cl-benzoate)4]·2CH3CN·2H2O (), where HL(sal-pyr), HL(sal-pip) and HL(sal-mor) are the 1 : 1 condensation products of salicylaldehyde and 1-(2-aminoethyl)-pyrrolidine, 1-(2-aminoethyl)-piperidine and 4-(2-…

Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co(II)6Co(III)3} and {Co(II)Co4(III)} mixed valent complexes and a study o…

2015

We are reporting two new mixed valent Co(ii)/Co(iii) polynuclear complexes, {Co II 6 Co III 3 } and {Co II Co III 4 }, bearing different amount of Co(ii) ions in their cores, through the employment of the multidentate triethanolamine (teaH 3 ) ligand in different stoichiometric ratios. We present a complete picture of the magnetic behaviour of both complexes through a combined usage of the susceptibility, magnetization and X-band EPR data as well as broken-symmetry DFT calculations. Compound 1 shows an atypical spin-only behaviour, probably due to the presence of four and five coordinated Co(ii) sites as well as highly distorted six coordinated Co(ii) ions, promoting a high degree of orbita…

Syntheses, structures, and magnetic properties of diphenoxo-bridged Cu(II)Ln(III) and Ni(II)(low-spin)Ln(III) compounds derived from a compartmental …

2010

Syntheses, characterization, and magnetic properties of a series of diphenoxo-bridged discrete dinuclear M(II)Ln(III) complexes (M = Cu or Ni, Ln = Ce-Yb) derived from the compartmental Schiff base ligand, H(2)L, obtained on condensation of 3-ethoxysalicylaldehyde with trans-1,2-diaminocyclohexane, are described. Single crystal X-ray structures of eight Cu(II)Ln(III) compounds (Ln = Ce (1), Pr (2), Nd (3), Sm (4), Tb (7), Ho (9), Er (10), and Yb (12)) and three Ni(II)Ln(III) (Ln = Ce (13), Sm (16), and Gd (18)) compounds have been determined. Considering the previously reported structure of the Cu(II)Gd(III) (6) compound (Eur. J. Inorg. Chem. 2005, 1500), a total of twelve structures are di…

Mononuclear and tetranuclear Fe(III) complexes with two different types of N, O donor Schiff base ligands

2013

Abstract A mononuclear Fe(III) complex of a tetradentate N 2 O 2 donor Schiff base ligand derived from 3-ethoxysalicaldehyde and ethylenediamine has been reported. In addition two tetranuclear Fe(III) complexes with discrete Fe 4 III (μ 4 -O) cores have been synthesized and characterized using two Schiff base ligands (H 2 L 1–2 ) derived from two different aromatic acid hydrazides and diacetyl monoxime. The mononuclear Fe(III) and one of the tetranuclear Fe(III) complexes have been structurally characterized by single-crystal X-ray crystallography. The mononuclear complex has a highly distorted octahedral geometry. The tetranuclear Fe(III) complexes are found to be rare examples with discre…

Expanding the 2, 2’-bipyrimidine bridged 1D homonuclear coordination polymers family: [MIIbpymCl2] (M=Fe, Co) magnetic and structural characterization

2013

One pot reaction of hydrated chloride salts of Fe(II) and Co(II) with stoichiometric amounts of 2, 2’-bipyrimidine (bpym) in a methanol/ acetonitrile mixture afforded the corresponding 1D homonuclear coordination polymers, [μ-(bpym)MCl2]n. Crystal structures of both complexes are isomorphous in the highly symmetric orthorhombic space group Fddd. The 1D coordination polymers are composed of almost orthogonal alternating bipyrimidine bridges linking the {MCl2} units. The magnetic behaviour of the Fe(II)compound can be well understood as a uniform S=2 chain with antiferromagnetic exchange interaction between metal ion sites. In the case of the Co(II) ion, also an antiferromagnetic interaction …

Synthesis and Structure of a Potassium Potassiochromate: A Bis-Chromium(II) Molecule Held Together by Near-Square-Planar Potassium−Ligand Bridges

2010

No Cr-Cr bonding is found in a new type of mixed-metal ate complex having two coordinatively unsaturated but sterically saturated bisamido-monoalkyl Cr(II) groups linked via an unusual near-square-planar-coordinated K atom in the moiety of the ate, while the cationic moiety is a separated iris-tmeda solvated second potassium atom.

Filling the Gap in the Metallacrown Family: The 9‐MC‐3 Chromium Metallacrown

2021

Abstract In this work, we report on a long‐sought missing complex in the metallacrown family. We synthesized and characterized the novel chromium metallacrown (MC) complex {CrIII(μ 2‐piv)3[9‐MCCr(III)N(shi)‐3](morph)3}⋅MeOH (in which shi3−=salicyl hydroxamate, piv=pivalate, and morph=morpholine). The MC with a 9‐MC‐3 cavity of kinetically inert chromium(III) ions was synthesized by a solvothermal reaction. Magnetization measurements reveal a high spin ground state.

Syntheses, Structures, Magnetic Properties, and Density Functional Theory Magneto-Structural Correlations of Bis(μ-phenoxo) and Bis(μ-phenoxo)-μ-acet…

2013

The bis(mu-phenoxo) (FeNiIII)-Ni-II compound [Fe-III(N-3)(2)LNiII(H2O)(CH3CN)](ClO4) (1) and the bis(mu-phenoxo)-mu-acetate/bis(mu-phenoxo)-bis(mu-acetate) (FeNiII)-Ni-III compound {[Fe-III(OAc)LNiII(H2O)(mu-OAc)](0.6)center dot[(FeLNiII)-L-III(mu-OAc)(2)](0.4)}(ClO4)center dot 1.1H(2)O (2) have been synthesized from the Robson type tetraiminodiphenol macrocyclic ligand H2L, which is the [2 + 2] condensation product of 4-methyl-2,6-diformylphenol and 2,2'-dimethy1-1,3-diaminopropane. Single-crystal X-ray structures of both compounds have been determined. The cationic part of the dinuclear compound 2 is a cocrystal of the two species [Fe-III(OAc)LNiII(H2O)(mu-OAc)](+) (2A) and [(FeLNiII)-L-I…

DFT broken-symmetry exchange couplings calculation in a 1D chain of bridged iron basic carboxylates

2009

DFT broken-symmetry calculations at the B3LYP level were carried out to evaluate the exchange coupling constants defined by the Heisenberg-Dirac-van Vleck spin Hamiltonian (HDvV), Ĥ = -2JŜaŜb, in a 1D chain of iron basic carboxylate cores [Fe3O(Piv)6(H2O)] bridged by dicyanamide, and two related trinuclear Fe3O moieties. The chain complex was modeled as two Fe3O units that preserve all features of the repetitive unit in the infinite real system. All geometries were taken from the crystallographic data previously reported. The obtained calculated values for the J constants are in good agreement with experimental results. The weak anti-ferromagnetic inter-Fe3O core interaction along the chain…

New complexes of Ni(II) and Co(III) with a Schiff-base ligand derived from o -vanillin. Crystal structure, magnetic and catalytic properties of a dis…

2018

Abstract A binuclear complex, [Ni2L2(NO3)(H2O)(CH3CN)]ClO4·CH3CN (1), has been obtained using a Schiff-base ligand (HL) derived from o-vanillin and 4-(2-aminoethyl)morpholine. The crystal structure of 1 has been solved. Both Ni(II) ions are hexacoordinated, but they display different coordination spheres. The exchange interaction between the two nickel ions is antiferromagnetic (J = −7.9 ± 0.2 cm−1; H = −JS1S2), in line with the DFT calculations. Compound 1 has been tested as a catalyst in the epoxidation of various olefins. The reaction of the same ligand with a mixture of cobalt(II) perchlorate and nitrate affords a mononuclear Co(III) complex, [CoL2(H2O)]ClO4·CH3OH (2).

Coordination versatility of 1,5-bis(salicylidene)carbohydrazide in Ni(II) complexes

2014

Abstract Versatile coordination behavior of a polydentate Schiff base ligand 1,5-bis(salicylidene)carbohydrazide (H3bsc) has been explored in Ni(II) complexes. [Ni(H3bsc)2](ClO4)2 (1)·H2O·3CH3CN is a bis chelate mononuclear complex of H3bsc in keto form, and [Ni4(H0.5bsc)2(O2CCMe3)3(CH3OH)4](2)·2H2O·2CH3OH is a tetranuclear complex of H3bsc with an unusual coordination. In 2, one phenolate group of the ligand coordinates in a monodentate way and the other coordinates in a μ2-bridging mode to the Ni(II) center. This unusual coordination mode of the ligand stabilizes the Ni(II) complex in a tetranuclear form where the carbonyl oxygen of the ligand exists in between keto and enol form of bond …

NaI/CuI–II heterometallic cages interconnected by unusual linear 2-coordinate OCN-Cu(I)-NCO links: synthesis, structural, magnetostructural correlati…

2009

A new Na(I)/Cu(I-II) heterometallic coordination complex [Cu(2)L(2)Na(NCO)(2)Cu](n) (1) with an unusual architecture has been synthesised. In 1 cyclic Na-O-Cu-O-Cu cages constructed by the tetradentate N(2)O(2) donor Schiff base ligand (H(2)L = N, N'-bis(2-hydroxyacetophenone) propylenediimine) are interconnected to each other by a rare singly end-to-end bridged OCN-Cu(I)-NCO link generating 1D chain. The complex has been characterised by elemental, spectral and structural analysis. The cyclic voltammogram of 1 has been compared with the analogous complexes. Cryomagnetic susceptibility studies indicate the copper(II) centers in the cyclic Na-O-Cu-O-Cu cages are antiferromagnetically coupled…

Sodium Congener of the Classical Lithium Methylchromate Dimer: Synthetic, X-ray Crystallographic, and Magnetic Studies of Me8Cr2[Na(OEt2)]4

2011

One of the milestone structures in the development of transition-metal complexes with metal metal bonds of multiple bond order was the lithium methylchromate dimer Me8Cr2[Li(donor)](4) (donor = THF or Et2O). Using a simple salt metathesis reaction mixing this compound with sodium tert-butoxide, the sodium congener Me8Cr2-[Na(OEt2)]4 has been synthesized as a green crystalline compound and isolated in 51% yield. Its solid-state structure was determined by single-crystal X-ray diffraction. Exhibiting exact crystallographic C-4h symmetry, this heavier alkali-metal chromate structure is also dimeric, formally comprising a (Me8Cr4)(4-) tetranionic core with four peripheral Na+ cations carrying s…

Coordination of expanded terpyridine ligands to cobalt

2013

Abstract The tridentate expanded terpyridine-like ligand N,N′-dimethyl-N,N′-dipyridin-2-yl-pyridin-2,6-diamine (ddpd) and [Co(H2O)6](BF4)2 give the high-spin complex mer-[Co(ddpd)2](BF4)2 with a tetragonally compressed CoN6 coordination geometry according to X-ray diffraction and SQUID measurements. UV–Vis–NIR spectra indicate a large ligand field splitting close to the high-spin/low-spin crossover point. Oxidation of the CoII complex to CoIII is achieved with silver triflate. The self exchange between high-spin CoII and low-spin CoIII is slow on the NMR time scale.

Synthesis, characterization, X-ray crystallography, and antimicrobial activities of Ni(II) and Cu(II) complexes with a salicylaldehyde-based thiosemi…

2014

A new salicylaldehyde-based ‘ONS’ tridentate salicylaldehyde-N(4)-diethylthiosemicarbazone (H2SANEt2) has been synthesized and characterized by elemental analyses, mass, IR, and 1H NMR spectral parameters. The coordination mode of the synthesized ligand is reported by solid state isolation and physico-chemical identification of Ni(II) and Cu(II) complexes, [Ni(SANEt2)]2 (1) and [Cu(SANEt2)]2 (2). Both complexes are neutral and oxygen-bridged dinuclear species. The ligand is bideprotonated ‘ONS’ tridentate in both complexes. IR spectral data indicate that coordination of each metal of the two complexes occurs through phenolic oxygen, azomethine nitrogen, and thiolato sulfur. X-ray crystallog…

Broken symmetry states of metallacrowns: Distribution of spins and the g tensor

2019

Magnetic and Spectroscopic Study on a New Asymmetric Mixed-valence Mn2(II,III) Coordination Compound

2015

A new dinuclear mixed-valence compound [MnIIMnIII(bttpnol)(O2C–C6H4–NO2)2]ClO4 was synthesized by using the asymmetric heptadentate ligand N-(2-hydroxybenzyl)-N,N′,N′-tris(2-pyridylmethyl)-1,3-diaminopropan-2-ol (H2btppnol). One central manganese atom assumes N3O3 and the other N2O4 coordination sphere. Both manganese ions are bridged by the alkoxy-group of the dinucleating ligand and two bidentate carboxylate groups of the nitrobenzoate ligands. The structural data show clearly that MnIII prefers the more oxygen rich donor set. Cyclic voltammetry measurements reveal that the mixed-valence state Mn2(II,III) could be reduced to Mn2(II,II) at E1/2(1) = –0.53 V and oxidized to Mn2(III,III) at …

Experimental and Theoretical Studies on Magnetic Exchange in Silole-Bridged Diradicals.

2006

International audience; Five bis(tert-butylnitroxide) diradicals connected by a silole [2,5-R2-3,4-diphenylsilole; R = Me3CN(®O.bul.)Z; Z = p-C6H4 (7a), p-C6H4C6H4-p (7b), 1,4-naphthalenediyl (7c), m-C6H4 (7d)] or a thiophene [2,5-R2-thiophene; R = p-Me3CN(®O.bul.)C6H4 (12)] ring as a coupler were studied. Compd. 12 crystallizes in the orthorhombic space group Pna21 with a 20.752(5), b 5.826(5), and c 34.309(5) .ANG.. X-ray crystal structure detn., electronic spectroscopy, variable-temp. EPR spectroscopy, SQUID measurements and DFT computations (UB3LYP/6-31+G*) were used to study the mol. conformations and electronic spin coupling in this series of mols. Whereas compds. 7b, 7c, and 7d are q…

Solvent-dependent SCO Behavior of Dinuclear Iron(II) Complexes with a 1,3,4-Thiadiazole Bridging Ligand

2016

Two dinuclear iron(II) complexes [Fe2(μ-L)2]X4*4DMF (X = BF4(-) (1·4DMF) and ClO4(-) (2·4DMF)) with a 1,3,4-thiadiazole bridging ligand have been synthesized and show a very distinct solvent-depending SCO behavior. The complexes represent new solvatomorphs of the first dinuclear iron(II) complexes with the ligand L (2,5-bis[(2-pyridylmethyl)amino]methyl-1,3,4-thiadiazole). The incorporated lattice DMF molecules directly affect the spin state of these complexes. This behavior reveals a structural insight into the role of the solvent molecules on the spin transition.

Structural, magnetic and electronic characterization of an isostructural series of dinuclear complexes of 3d metal ions bridged by tpbd

2013

Abstract Dinuclear complexes of the type [{M(H2O)(phen)}2(μ-tpbd)](ClO4)4 with N,N,N′,N′-Tetrakis-(2-pyridylmethyl)-benzene-1,4-diamine (tpbd) as bridging ligand and M = Mn(II) (1), Fe(II) (2), Co(II) (3), Ni(II) (4), Cu(II) (5), Zn(II) (6) were synthesized, structurally analyzed and their magnetic as well as their electrochemical properties are determined. A ligand-centered one-electron oxidation leads to radical complexes for which the lifetimes are strongly dependent on the coordinated metal ion as followed from time-resolved UV–Vis absorption spectroscopy. In addition to the six homometallic dinuclear complexes, one analog heterometallic Mn(II)/Ni(II) compound (7) of the same constituti…

Integrated experimental and computational spectroscopy study on the protonation of the α-nitronyl nitroxide radical unit

2011

The stability of the α-nitronyl nitroxide radical unit under acidic conditions is investigated by an integrated experimental UV/Vis spectroscopy and TDDFT study. In the field of molecular magnetism, α-nitronyl nitroxide radicals are important as purely organic spin carriers due to their synthetic versatility. Here, the existence of an intermediate of the protonated α-nitronyl nitroxide radical unit is demonstrated for the first time and a proposed disproportionation reaction is confirmed.

A Family of Dinuclear Iron(II) SCO Compounds Based on a 1,3,4‐Thiadiazole Bridging Ligand

2015

A new family of dinuclear iron(II) spin-crossover (SCO) compounds with the formula [Fe2(μ-L)2]X4, with three different counteranions [X = BF4– (1), ClO4– (2) and F3CSO3– (3)], was prepared and characterized by single-crystal X-ray diffraction, variable-temperature magnetic susceptibility and Mossbauer measurements. These are the first dinuclear iron(II) SCO complexes with a 1,3,4-thiadiazole bridging ligand L {with L = 2,5-bis[(2-pyridylmethyl)amino]methyl-1,3,4-thiadiazole}. The magnetic measurements reveal a gradual and incomplete SCO of the three compounds around room temperature, starting from a diamagnetic [LS–LS] state. The diamagnetic ground state is in agreement with the single-crys…

Cover Picture: Direct CH Metalation with Chromium(II) and Iron(II): Transition-Metal Host / Benzenediide Guest Magnetic Inverse-Crown Complexes (Ang…

2009

Chromation and ferration are the latest additions to the concept of alkali-metal-mediated metalation, as described by J. Klett, R. E. Mulvey, and co-workers in their Communication on page 3317 ff. While the more electropositive sodium is essential for the reaction, it is the less electropositive chromium or iron that actually performs deprotonation of benzene. This novel reactivity can be likened to a game of chess in which the queen (Na) holds the king in check, while the knight (Cr, Fe) scores checkm(etal)ate.

Direct C-H metalation with chromium(ii) and iron(ii): transition- metal host/benzenediide guest magnetic inverse-crown complexes

2009

Check M(etal)ate: The chessboard and the figures represent a special reaction in which different low-polarity metals can metalate arenes directly when they are brought into the right position. In a combination of queen (sodium) and knight (chromium or iron), it is possible for the knight (usually the weaker piece) to make a direct deadly hit on the king (benzene) in this game of elemental chess. Fil: Alborés, Pablo. Johannes Gutenberg Universitat Mainz; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Carrella, Luca M.. Johannes Gutenberg Universitat Mainz; Alemania Fil: Clegg, William. University of Newcastle; Reino Unido Fil: García Álvarez, Pablo. Univ…

The Interplay of Hydrogen Bonding and Multiple Metal Binding – A New Cyclic Polyaminopolyalcohol Ligand as Building Block for the Construction of Mic…

2011

Cyclohexane-based polyaminopolyalcohols (PAPAs) such as 1,3-diamino-1,2,3-trideoxy-cis-inositol (daci) have been prepared by hydrogenation of suitable aromatic precursors. The pentanuclear complex [Cu5(daci)4(H–2daci)2](SO4)3·18H2O (C3) revealed antiferromagnetic and ferromagnetic interactions between the CuII centers with an S = 3/2 ground state. The microporous structure of C3 exhibited a dehydration/rehydration reaction with an entirely amorphous dehydrated phase at 150 °C and a completely reversible rehydration process at 30 °C. The potential of PAPA ligands for forming polynuclear complexes and supramolecular, hydrogen-bonded networks is discussed.

3d/4f Sandwich Complex Based on Metallacrowns.

2021

A novel lanthanide double-decker complex with nickel metallacrowns (MCs) as coordinating ligands has been synthesized. In the 3d/4f metallacrown complex TbIII[12-MCNiIIN(shi)-4]2, the central lanthanide ion is sandwiched between two [12-MC-4] units, forming an almost ideal square-antiprismatic coordination sphere. The resulting zenithal angles at the central lanthanide ion are smaller than those for previously reported sandwich compounds. Magnetic measurements reveal an energy barrier of 346 K under zero field and up to 585 K under 3200 Oe, the highest reported for metallacrowns with D4d symmetry.

Control of Exchange Interactions in Trinuclear Complexes Based on Orthogonal Magnetic Orbitals

2009

The reaction of copper(II) acetate with the tetradentate Schiff base like ligand H4L {(E,E)-[{diethyl 2,2′-[4,5-dihydroxy-1,2-phenylenebis(iminomethylidyne)]bis(3-oxobutanoate)}] leads to the formation of the square planar N2O2 coordinated complex [H2CuL]. Reaction of two equivalents of this complex with copper(II) acetylacetonato or vanadyl(IV) acetylacetonato yields the trinuclear complexes [V(O)Cu2L2][N(nBu)4]2·2MeOH (1) and [Cu3L2][N(nBu)4]2·2DMF (2). Both complexes were characterised by using magnetic measurements and X-ray crystallography. Special attention was given to the spin-exchange coupling through the bridging phenylene ring. The principle of strict orthogonality of the magneti…

Azide bridged dicopper(II), dicobalt(II) complexes and a rare double μ-chloride bridged ferromagnetic dicobalt(II) complex of a pyrazolyl-pyrimidine …

2012

Abstract Two new dinuclear copper(II) complexes [Cu2(PymPz)2(N3)2Cl2] (1), [Cu2(PymPz)2(N3)4] (2) and two new dinuclear cobalt(II) complexes [Co2(PymPz)2Cl4] (3), [Co2(PymPz)2(N3)4] (4) [PymPz = 2-(3,5-dimethyl-1H-pyrazol-1-yl)-4,6-dimethylpyrimidine] have been synthesized and characterized crystallographically and spectroscopically. In each of the complexes 1, 2 and 4 the two adjacent metal centers are bridged by a pair of μ-1,1 azide groups whereas in 3 the metal centers are bridged by a pair of chloride ions. In the complexes, all the metal centers are pentacoordinated. In 1 and 2 the copper(II) centers have distorted square pyramidal geometry (τ = 0.18 for 1 and 0.091 for 2) but in 3 an…

A Tetracopper(II)-Tetraradical Cuboidal Core and Its Reactivity as a Functional Model of Phenoxazinone Synthase

2007

The coordination chemistry of the tridentate ligand N-(2-hydroxy-3,5-di-tert-butylphenyl)-2-aminobenzylalcohol H3L has been studied with the copper(II) ion. The ligand is noninnocent in the sense that it is readily oxidized in the presence of air to its o-iminobenzosemiquinonato [L*]2- radical form. The crystal structure of the synthesized tetracopper(II)-tetraradical complex [CuII4(L*)4] (1), has been determined by X-ray crystallography at 100 K. Variable-temperature (2-290 K) magnetic susceptibility measurements of complex 1 containing eight paramagnetic centers establish the spin ground state to be diamagnetic (St=0) arising from the antiferromagnetic interactions. Electrochemical measur…

Structural and Magnetic Insights into the Trinuclear Ferrocenophane and Unexpected Hydrido Inverse Crown Products of Alkali‐Metal‐Mediated Manganatio…

2008

With the aim of introducing the diisopropylamide [NiPr(2)](-) ligand to alkali-metal-mediated manganation (AMMMn) chemistry, the temperature-dependent reactions of a 1:1:3 mixture of butylsodium, bis(trimethylsilylmethyl)manganese(II), and diisopropylamine with ferrocene in hexane/toluene have been investigated. Performed at reflux temperature, the reaction affords the surprising, ferrocene-free, hydrido product [Na(2)Mn(2) (mu-H)(2){N(iPr)(2)}(4)]2 toluene (1), the first Mn hydrido inverse crown complex. Repeating the reaction rationally, excluding ferrocene, produces 1 in an isolated crystalline yield of 62 %. At lower temperatures, the same bimetallic amide mixture leads to the manganati…

Copper(II) complexes with 1,5-bis(2-hydroxybenzaldehyde)carbohydrazone

2014

Abstract The acid–base properties of 1,5-bis(2-hydroxybenzaldehyde)carbohydrazone (H4L) and its thioanalogue 1,5-bis(2-hydroxybenzaldehyde)thiocarbohydrazone (H4LS) have been studied experimentally by pH-potentiometry and UV–Vis spectrophotometry and theoretically by using DFT methods. Copper(II) complexes [Cu2(HL)(DMSO)2(H2O)]NO3·H2O (1), [{Cu2(HL)(DMF)(H2O)}n][{Cu2(HL)(DMF)NO3}n](NO3)n (2), [Cu2(HL)(DMF)2(H2O)]HSO4·H2O (3), [Cu2(HL)(DMF)2(H2O)][Cu2(HL)(SO4)(H2O)(DMF)2]·2H2O (4) and [Cu4(HL)2(HSO4)(DMF)2]HSO4 (5), where H4L = 1,5-bis(2-hydroxybenzaldehyde)carbohydrazone, have been synthesised. Complexes 1–3 have been characterised by elemental analysis, IR spectroscopy, ESI mass spectromet…

Enforcement of a high-spin ground state for the first 3d heterometallic 12-metallacrown-4 complex.

2014

Cu(II)(DMF)2Cl2[12-MC(Fe(III)N(Shi))-4](DMF)4·2DMF was synthesized as the first heterometallic transition metal 12-MC-4 complex. The purposeful placement of specific metal ions in the different sites of the metallacrown attains the establishment of a high-spin ground state. Inducing the anticipated superior exchange interactions, the central Cu(II) guest ion averts the common mutual cancellation of the spins, as is observed in the corresponding homometallic compounds.

CCDC 1825561: Experimental Crystal Structure Determination

2019

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CCDC 1431264: Experimental Crystal Structure Determination

2015

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CCDC 2044705: Experimental Crystal Structure Determination

2021

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CCDC 965183: Experimental Crystal Structure Determination

2014

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CCDC 1481090: Experimental Crystal Structure Determination

2016

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CCDC 1949845: Experimental Crystal Structure Determination

2020

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CCDC 1434704: Experimental Crystal Structure Determination

2016

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CCDC 1980403: Experimental Crystal Structure Determination

2020

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CCDC 977382: Experimental Crystal Structure Determination

2016

Related Article: Christoph Deckert, Denis Bittner, Luca M. Carrella, Dieter Schollmeyer and Eva Rentschler|2016|Eur.J.Inorg.Chem.||1738|doi:10.1002/ejic.201501400

CCDC 978467: Experimental Crystal Structure Determination

2014

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CCDC 1979793: Experimental Crystal Structure Determination

2020

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CCDC 1979785: Experimental Crystal Structure Determination

2020

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CCDC 2104301: Experimental Crystal Structure Determination

2021

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CCDC 1949842: Experimental Crystal Structure Determination

2020

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CCDC 999771: Experimental Crystal Structure Determination

2015

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CCDC 1481097: Experimental Crystal Structure Determination

2016

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CCDC 1876390: Experimental Crystal Structure Determination

2019

Related Article: Steffen Treiling, Cui Wang, Christoph Fçrster, Florian Reichenauer, Jens Kalmbach, Pit Boden, Joe P. Harris, Luca M. Carrella, Eva Rentschler, Ute Resch-Genger, Christian Reber, Michael Seitz, Markus Gerhards, and Katja Heinze|2019|Angew.Chem.,Int.Ed.|58|18075|doi:10.1002/anie.201909325

CCDC 1979783: Experimental Crystal Structure Determination

2020

Related Article: Elena A. Mikhalyova, Matthias Zeller, Jerry P. Jasinski, Raymond J. Butcher, Luca M. Carrella, Alexander E. Sedykh, Konstantin S. Gavrilenko, Sergey S. Smola, Michael Frasso, Sebastian Calderon Cazorla, Kuluni Perera, Anni Shi, Habib G. Ranjbar, Casey Smith, Alexandru Deac, Youlin Liu, Sean M. McGee, Vladimir P. Dotsenko, Michael U. Kumke, Klaus Müller-Buschbaum, Eva Rentschler, Anthony W. Addison, Vitaly V. Pavlishchuk|2020|Dalton Trans.|49|7774|doi:10.1039/D0DT00600A

CCDC 1027635: Experimental Crystal Structure Determination

2014

Related Article: Christian Plenk, Jasmin Krause, Eva Rentschler|2015|Eur.J.Inorg.Chem.||370|doi:10.1002/ejic.201402955

CCDC 1979777: Experimental Crystal Structure Determination

2020

Related Article: Elena A. Mikhalyova, Matthias Zeller, Jerry P. Jasinski, Raymond J. Butcher, Luca M. Carrella, Alexander E. Sedykh, Konstantin S. Gavrilenko, Sergey S. Smola, Michael Frasso, Sebastian Calderon Cazorla, Kuluni Perera, Anni Shi, Habib G. Ranjbar, Casey Smith, Alexandru Deac, Youlin Liu, Sean M. McGee, Vladimir P. Dotsenko, Michael U. Kumke, Klaus Müller-Buschbaum, Eva Rentschler, Anthony W. Addison, Vitaly V. Pavlishchuk|2020|Dalton Trans.|49|7774|doi:10.1039/D0DT00600A

CCDC 1481096: Experimental Crystal Structure Determination

2016

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CCDC 727665: Experimental Crystal Structure Determination

2015

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CCDC 1979787: Experimental Crystal Structure Determination

2020

Related Article: Elena A. Mikhalyova, Matthias Zeller, Jerry P. Jasinski, Raymond J. Butcher, Luca M. Carrella, Alexander E. Sedykh, Konstantin S. Gavrilenko, Sergey S. Smola, Michael Frasso, Sebastian Calderon Cazorla, Kuluni Perera, Anni Shi, Habib G. Ranjbar, Casey Smith, Alexandru Deac, Youlin Liu, Sean M. McGee, Vladimir P. Dotsenko, Michael U. Kumke, Klaus Müller-Buschbaum, Eva Rentschler, Anthony W. Addison, Vitaly V. Pavlishchuk|2020|Dalton Trans.|49|7774|doi:10.1039/D0DT00600A

CCDC 1587515: Experimental Crystal Structure Determination

2018

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CCDC 984042: Experimental Crystal Structure Determination

2014

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CCDC 1448813: Experimental Crystal Structure Determination

2016

Related Article: Christian F. Herold, Sergii I. Shylin, and Eva Rentschler|2016|Inorg.Chem.|55|6414|doi:10.1021/acs.inorgchem.6b00163

CCDC 977085: Experimental Crystal Structure Determination

2016

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CCDC 978468: Experimental Crystal Structure Determination

2014

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CCDC 1959867: Experimental Crystal Structure Determination

2020

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CCDC 928716: Experimental Crystal Structure Determination

2013

Related Article: Pablo Albores,Eva Rentschler|2013|Dalton Trans.|42|9621|doi:10.1039/C3DT50691F

CCDC 1481098: Experimental Crystal Structure Determination

2016

Related Article: Jacob Overgaard, Louise H. Møller, Mette A. Borup, Maxime Tricoire, James P. S. Walsh, Marcel Diehl, Eva Rentschler|2016|Dalton Trans.|45|12924|doi:10.1039/C6DT02024K

CCDC 1026942: Experimental Crystal Structure Determination

2014

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CCDC 1949843: Experimental Crystal Structure Determination

2020

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CCDC 903324: Experimental Crystal Structure Determination

2017

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CCDC 1979786: Experimental Crystal Structure Determination

2020

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CCDC 999768: Experimental Crystal Structure Determination

2015

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CCDC 1864765: Experimental Crystal Structure Determination

2018

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CCDC 1989536: Experimental Crystal Structure Determination

2021

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CCDC 2104300: Experimental Crystal Structure Determination

2021

Related Article: Peter Happ, Christian Plenk, Eva Rentschler|2015|Coord.Chem.Rev.|289-290|238|doi:10.1016/j.ccr.2014.11.012

CCDC 1489635: Experimental Crystal Structure Determination

2017

Related Article: Alejandro V. Funes, Luca Carrella, Yvonne Rechkemmer, Joris van Slageren, Eva Rentschler, Pablo Alborés|2017|Dalton Trans.|46|3400|doi:10.1039/C6DT04713K

CCDC 1587514: Experimental Crystal Structure Determination

2018

Related Article: Ai-Min Li, Tim Hochdoerffer, Juliusz A. Wolny, Volker Schuenemann, Eva Rentschler|2018|Eur.J.Inorg.Chem.|2018|4190|doi:10.1002/ejic.201800784

CCDC 1959865: Experimental Crystal Structure Determination

2020

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CCDC 978469: Experimental Crystal Structure Determination

2014

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CCDC 1958562: Experimental Crystal Structure Determination

2020

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CCDC 1489636: Experimental Crystal Structure Determination

2017

Related Article: Alejandro V. Funes, Luca Carrella, Yvonne Rechkemmer, Joris van Slageren, Eva Rentschler, Pablo Alborés|2017|Dalton Trans.|46|3400|doi:10.1039/C6DT04713K

CCDC 1587516: Experimental Crystal Structure Determination

2018

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CCDC 1478937: Experimental Crystal Structure Determination

2016

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CCDC 1488918: Experimental Crystal Structure Determination

2020

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CCDC 2078695: Experimental Crystal Structure Determination

2021

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CCDC 1434702: Experimental Crystal Structure Determination

2016

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CCDC 1979788: Experimental Crystal Structure Determination

2020

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CCDC 986866: Experimental Crystal Structure Determination

2014

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CCDC 2104296: Experimental Crystal Structure Determination

2021

Related Article: Peter Happ, Christian Plenk, Eva Rentschler|2015|Coord.Chem.Rev.|289-290|238|doi:10.1016/j.ccr.2014.11.012

CCDC 1026941: Experimental Crystal Structure Determination

2014

Related Article: Alejandro V. Funes, Luca Carrella, Lorenzo Sorace, Eva Rentschler, Pablo Alborés|2015|Dalton Trans.|44|2390|doi:10.1039/C4DT03034F

CCDC 1558560: Experimental Crystal Structure Determination

2017

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CCDC 961048: Experimental Crystal Structure Determination

2014

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CCDC 1979789: Experimental Crystal Structure Determination

2020

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CCDC 1062667: Experimental Crystal Structure Determination

2015

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CCDC 1873577: Experimental Crystal Structure Determination

2019

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CCDC 1949841: Experimental Crystal Structure Determination

2020

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CCDC 1481092: Experimental Crystal Structure Determination

2016

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CCDC 1825562: Experimental Crystal Structure Determination

2019

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CCDC 764821: Experimental Crystal Structure Determination

2013

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CCDC 808523: Experimental Crystal Structure Determination

2013

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CCDC 1980402: Experimental Crystal Structure Determination

2020

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CCDC 986867: Experimental Crystal Structure Determination

2014

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CCDC 1048420: Experimental Crystal Structure Determination

2015

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CCDC 958224: Experimental Crystal Structure Determination

2013

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CCDC 961049: Experimental Crystal Structure Determination

2014

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CCDC 1829268: Experimental Crystal Structure Determination

2018

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CCDC 1558856: Experimental Crystal Structure Determination

2017

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CCDC 978061: Experimental Crystal Structure Determination

2014

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CCDC 2093069: Experimental Crystal Structure Determination

2021

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CCDC 986871: Experimental Crystal Structure Determination

2014

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CCDC 910513: Experimental Crystal Structure Determination

2015

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CCDC 1979781: Experimental Crystal Structure Determination

2020

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CCDC 1048423: Experimental Crystal Structure Determination

2015

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CCDC 1980401: Experimental Crystal Structure Determination

2020

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CCDC 2078697: Experimental Crystal Structure Determination

2021

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CCDC 1462510: Experimental Crystal Structure Determination

2016

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CCDC 978470: Experimental Crystal Structure Determination

2014

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CCDC 1979776: Experimental Crystal Structure Determination

2020

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CCDC 1431266: Experimental Crystal Structure Determination

2015

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CCDC 2083757: Experimental Crystal Structure Determination

2021

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CCDC 999772: Experimental Crystal Structure Determination

2015

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CCDC 1481094: Experimental Crystal Structure Determination

2016

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CCDC 2104302: Experimental Crystal Structure Determination

2021

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CCDC 1048421: Experimental Crystal Structure Determination

2015

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CCDC 2104297: Experimental Crystal Structure Determination

2021

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CCDC 977386: Experimental Crystal Structure Determination

2016

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CCDC 977380: Experimental Crystal Structure Determination

2016

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CCDC 1815494: Experimental Crystal Structure Determination

2018

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CCDC 1826839: Experimental Crystal Structure Determination

2018

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CCDC 1434703: Experimental Crystal Structure Determination

2016

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CCDC 1873578: Experimental Crystal Structure Determination

2019

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CCDC 977362: Experimental Crystal Structure Determination

2014

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CCDC 2010168: Experimental Crystal Structure Determination

2022

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CCDC 942761: Experimental Crystal Structure Determination

2013

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CCDC 1979790: Experimental Crystal Structure Determination

2020

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CCDC 1048422: Experimental Crystal Structure Determination

2015

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CCDC 903325: Experimental Crystal Structure Determination

2017

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CCDC 1870627: Experimental Crystal Structure Determination

2018

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CCDC 1558855: Experimental Crystal Structure Determination

2017

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CCDC 1431263: Experimental Crystal Structure Determination

2015

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CCDC 961050: Experimental Crystal Structure Determination

2014

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CCDC 1869182: Experimental Crystal Structure Determination

2018

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CCDC 1481084: Experimental Crystal Structure Determination

2016

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CCDC 977406: Experimental Crystal Structure Determination

2016

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CCDC 1958093: Experimental Crystal Structure Determination

2020

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CCDC 977392: Experimental Crystal Structure Determination

2016

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CCDC 1062665: Experimental Crystal Structure Determination

2015

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CCDC 999770: Experimental Crystal Structure Determination

2015

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CCDC 816865: Experimental Crystal Structure Determination

2014

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CCDC 2044706: Experimental Crystal Structure Determination

2021

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CCDC 1870629: Experimental Crystal Structure Determination

2018

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CCDC 1481089: Experimental Crystal Structure Determination

2016

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CCDC 1989537: Experimental Crystal Structure Determination

2021

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CCDC 1481088: Experimental Crystal Structure Determination

2016

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CCDC 2078699: Experimental Crystal Structure Determination

2021

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CCDC 1979782: Experimental Crystal Structure Determination

2020

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CCDC 1979775: Experimental Crystal Structure Determination

2020

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CCDC 2104303: Experimental Crystal Structure Determination

2021

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CCDC 986869: Experimental Crystal Structure Determination

2014

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CCDC 1481086: Experimental Crystal Structure Determination

2016

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CCDC 1558561: Experimental Crystal Structure Determination

2017

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CCDC 984043: Experimental Crystal Structure Determination

2014

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CCDC 1481085: Experimental Crystal Structure Determination

2016

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CCDC 1839534: Experimental Crystal Structure Determination

2018

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CCDC 1876389: Experimental Crystal Structure Determination

2019

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CCDC 1903450: Experimental Crystal Structure Determination

2019

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CCDC 1870630: Experimental Crystal Structure Determination

2021

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CCDC 2078698: Experimental Crystal Structure Determination

2021

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CCDC 1959866: Experimental Crystal Structure Determination

2020

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CCDC 1873576: Experimental Crystal Structure Determination

2019

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CCDC 2104295: Experimental Crystal Structure Determination

2021

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CCDC 1481093: Experimental Crystal Structure Determination

2016

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CCDC 1959864: Experimental Crystal Structure Determination

2020

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CCDC 965184: Experimental Crystal Structure Determination

2014

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CCDC 1864766: Experimental Crystal Structure Determination

2018

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CCDC 978062: Experimental Crystal Structure Determination

2014

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CCDC 1938756: Experimental Crystal Structure Determination

2019

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CCDC 1870628: Experimental Crystal Structure Determination

2018

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CCDC 1481095: Experimental Crystal Structure Determination

2016

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CCDC 2010169: Experimental Crystal Structure Determination

2021

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CCDC 1431265: Experimental Crystal Structure Determination

2015

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CCDC 1489634: Experimental Crystal Structure Determination

2017

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CCDC 1864767: Experimental Crystal Structure Determination

2018

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CCDC 2078696: Experimental Crystal Structure Determination

2021

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CCDC 1489637: Experimental Crystal Structure Determination

2017

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CCDC 1979780: Experimental Crystal Structure Determination

2020

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CCDC 1815493: Experimental Crystal Structure Determination

2018

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CCDC 999769: Experimental Crystal Structure Determination

2015

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CCDC 978466: Experimental Crystal Structure Determination

2014

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CCDC 984713: Experimental Crystal Structure Determination

2014

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CCDC 928717: Experimental Crystal Structure Determination

2013

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CCDC 986865: Experimental Crystal Structure Determination

2014

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CCDC 816864: Experimental Crystal Structure Determination

2014

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CCDC 1979791: Experimental Crystal Structure Determination

2020

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CCDC 2044707: Experimental Crystal Structure Determination

2021

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CCDC 977454: Experimental Crystal Structure Determination

2016

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CCDC 1873575: Experimental Crystal Structure Determination

2019

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CCDC 1979794: Experimental Crystal Structure Determination

2020

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CCDC 2104298: Experimental Crystal Structure Determination

2021

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CCDC 2104299: Experimental Crystal Structure Determination

2021

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CCDC 1815495: Experimental Crystal Structure Determination

2018

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CCDC 1434701: Experimental Crystal Structure Determination

2016

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CCDC 1481083: Experimental Crystal Structure Determination

2016

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CCDC 1949844: Experimental Crystal Structure Determination

2020

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CCDC 986870: Experimental Crystal Structure Determination

2014

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CCDC 764822: Experimental Crystal Structure Determination

2013

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CCDC 1448812: Experimental Crystal Structure Determination

2016

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CCDC 919439: Experimental Crystal Structure Determination

2013

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CCDC 1979778: Experimental Crystal Structure Determination

2020

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CCDC 1979784: Experimental Crystal Structure Determination

2020

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CCDC 1481087: Experimental Crystal Structure Determination

2016

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CCDC 986868: Experimental Crystal Structure Determination

2014

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CCDC 1062666: Experimental Crystal Structure Determination

2015

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CCDC 977381: Experimental Crystal Structure Determination

2016

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CCDC 1825560: Experimental Crystal Structure Determination

2019

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CCDC 1481091: Experimental Crystal Structure Determination

2016

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CCDC 1979779: Experimental Crystal Structure Determination

2020

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CCDC 1979792: Experimental Crystal Structure Determination

2020

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CCDC 919440: Experimental Crystal Structure Determination

2013

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CCDC 1489638: Experimental Crystal Structure Determination

2017

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CCDC 986872: Experimental Crystal Structure Determination

2014

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CCDC 1587517: Experimental Crystal Structure Determination

2018

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CCDC 2047296: Experimental Crystal Structure Determination

2021

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CCDC 1950549: Experimental Crystal Structure Determination

2019

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CCDC 2104304: Experimental Crystal Structure Determination

2021

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