Search results for "Graph"

Self‐Assembly and Characterisation of Grid‐Type Iron( II ), Cobalt( II ) and Zinc( II ) Complexes

2003

The reaction of the ligands 5 and 6, containing two tridentate binding units, with iron(II), cobalt(II) and zinc(II) leads to the self-assembly of supramolecular architectures of [2 × 2] grid type containing four ions in octahedral coordination sites. The grid-type structures have been assigned on the basis of the spectroscopic data in solution, and confirmed in the solid state in the case of complexes 6b and 6c by X-ray crystallography. The latter study revealed that each metal ion is situated in a distorted octahedral coordination environment comprising two N,N,O ligand donor sets. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

On the magneto-structural role of the coordinating anion in oxamato-bridged copper(ii) derivatives

2019

We herein present the synthesis, spectroscopic analysis, description of the crystal structures and magnetic properties of four new complexes of the formula [{Cu(opba)(H2O)1.2}{Cu(dmphen)(SCN)}2]·dmf (1), [{Cu(opba)}2{Cu(dmphen)Cl}4]·1.5dmf·2.5dmso (2), [{Cu(opba)}2{Cu(dmphen)Br}4]·dmf·2.3dmso (3) and [{Cu(opba)}{Cu(dmphen)(dca)}2]n (4) [H4opba = N,N′-1,2-phenylenebis(oxamic acid), dmphen = 2,9-dimethyl-1,10-phenanthroline and dca = dicyanamide anion]. 1 is a neutral tricopper(II) complex where an inner [Cu(opba)]2− fragment adopts a bis-bidentate coordination mode towards two outer [Cu(dmphen)(NCS)]+ units. 2 and 3 are bis-trinuclear species where two oxamato-bridged [Cu(opba){Cu(dmphen)X}2…

Effects of Remote Ligand Substituents on the Structures, Spectroscopic, and Magnetic Properties of Two-Coordinate Transition-Metal Thiolate Complexes

2018

The first-row transition-metal(II) dithiolates M(SAriPr4)2 [AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2; M = Cr (1), Mn (3), Fe (4), Co (5), Ni (6), and Zn (7)] and Cr(SArMe6)2 [2; ArMe6 = C6H3-2,6-(C6H2-2,4,6-Me3)2] and the ligand-transfer reagent (NaSAriPr4)2 (8) are described. In contrast to their M(SAriPr6)2 (M = Cr, Mn, Fe, Co, Ni, and Zn; AriPr6 = C6H3-2,6-(C6H2-2,4,6-iPr3)2) congeners, which differ from 1 and 3-6 in having p-isopropyl groups on the flanking aryl rings of the terphenyl substituents, compounds 1 and 4-6 display highly bent coordination geometries with S-M-S angles of 109.802(2)° (1), 120.2828(3)° (4), 91.730(3)° (5), and 92.68(2)° (6) as well as relatively close metal-flanking …

A carboxylate-bridged NiII8 cluster with a distorted cubane topology: structure, magnetism and density functional studies

2016

Using a dicarboxylate ligand appended with (2-pyridyl)ethylamine unit, a new cluster [NiII8(L4)6(DMF)2(CH3OH)2(H2O)6][ClO4]4·2CH3OH·2CH3CO2C2H5 (1) [L4(2−): 3-[N-{2-(pyridin-2-yl)ethyl}amino]-bis(propionate)] has been synthesized, through ‘coordination-driven self-assembly’. The crystal structure of 1 reveals a centrosymmetric octanuclear carboxylate-bridged nickel(II) tetracation, with a distorted cubane topology. The four crystallographically independent nickel(II) centres differ markedly in their coordination environment. Magnetic studies (2–300 K) reveal that in 1 the net magnetic-exchange is antiferromagnetic. Based on geometric parameters associated with two interacting nickel(II) cen…

CuII2, CuII4 and CuII6 complexes with 3-(2-pyridyl)pyrazolate. Structure, magnetism and core interconversion

2019

Abstract Reactions of stoichiometric amounts of L1(−) (HL1 = 3-(2-pyridyl)pyrazole) with [Cu(H2O)6](ClO4)2, with or without PhCO2−, in MeOH or N,N′-dimethylformamide (dmf), led to the isolation of three copper(II) complexes of varying nuclearity, [CuII2(L1)2(ClO4)2(MeOH)2] (1), [CuII4(L1)4(O2CPh)2(MeOH)4](ClO4)2·2H2O (2) and [CuII6(L1)6(O2CPh)2(ClO4)2(dmf)4](ClO4)2·2dmf·2H2O (3). Structural analysis reveals two centrosymmetric four-coordinate {CuII(L1)(ClO4)(MeOH)} units are dipyrazolate-bridged in 1, giving rise to a square-pyramidal (SP; τ = 0.13) coordination to the CuII ion. In 2, two centrosymmetric four-coordinate dipyrazolate-bridged {CuII2(μ-L1)2(MeOH)2}2+ units in two layers are he…

Oxygen Transfer from Trimethylamine N ‐Oxide to Cu I Complexes Supported by Pentanitrogen Ligands

2020

[N,N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L1) and [N,N-bis(2-quinolylmethyl)-N-bis(2-pyridyl)methylamine] (L2) were employed to prepare CuII and CuI complexes for spectroscopic and structural characterization. [L1CuII(H2O)](NO3)2 and [L2CuII(NO3)]NO3 have Jahn–Teller distorted octahedral geometries and give rise to isotropic EPR spectra in frozen solution. [L1CuI(CH3CN)]OTf and [L2CuI(CH3CN)]OTf have distorted trigonal bipyramidal and tetrahedral solid-state structures, respectively. The N-donors display labile behavior in solution, based on variable-temperature 1H NMR studies. Addition of trimethylamine N-oxide (Me3NO) to solutions of [L1CuI(CH3CN)]OTf and [L…

2015

The energy barrier to magnetisation relaxation in single-molecule magnets (SMMs) proffers potential technological applications in high-density information storage and quantum computation. Leading candidates amongst complexes of 3d metals ions are the hexametallic family of complexes of formula [Mn6O2(R-sao)6(X)2(solvent)y] (saoH2=salicylaldoxime; X=mono-anion; y=4–6; R=H, Me, Et, and Ph). The recent synthesis of cationic [Mn6][ClO4]2 family members, in which the coordinating X ions were replaced with non-coordinating anions, opened the gateway to constructing families of novel [Mn6] salts in which the identity and nature of the charge balancing anions could be employed to alter the physical…

N-Acyl-glutarimides: Effect of Glutarimide Ring on the Structures of Fully Perpendicular Twisted Amides and N–C Bond Cross-Coupling

2020

N-Acyl-glutarimides have emerged as the most reactive precursors for N-C(O) bond cross-coupling reactions to date, wherein the reactivity is driven by ground-state destabilization of the amide bond. Herein, we report a full study on the effect of a glutarimide ring on the structures, electronic properties, and reactivity of fully perpendicular N-acyl-glutarimide amides. Most notably, this report demonstrates the generality of deploying N-acyl-glutarimides to achieve full twist of the acyclic amide bond, and results in the discovery of N-acyl-glutarimide amide with an almost perfect twist value, τ = 89.1°. X-ray structures of five new N-acyl-glutarimides are reported. Reactivity studies in t…

N-Cobaltocenium Amide as Reactive Nucleophilic Reagent for Donor–Acceptor Bimetallocenes

2017

Deprotonation of the aminocobaltocenium ion [Cc-NH2]+ ([H-1]+) generates the nucleophilic imine CcNH (1). Reaction of 1 with acid chlorides R–COCl (R = Ph, Fc, and Cc+) yields the reference amide [Ph-CO-NH-Cc]+ (2+) and the amide-linked hetero- and homobimetallocenes [Fc-CO-NH-Cc]+ (3+) and [Cc-CO-NH-Cc]2+ (42+), respectively. Cation–anion interactions of charged amides 2+–42+ in the solid state and in solution are probed by single crystal X-ray diffraction and NMR and IR spectroscopy. Intramolecular metal–metal interactions in donor–acceptor heterobimetallocene 3+ and in mixed-valent homobimetallocene 4+ (prepared electrochemically) are discussed within the Marcus–Hush framework aided by s…

Size‐Selective Encapsulation of Hydrophobic Guests by Self‐Assembled M 4 L 6 Cobalt and Nickel Cages

2012

Subtle differences in metal-ligand bond lengths between a series of [M(4)L(6)](4-) tetrahedral cages, where M = Fe(II), Co(II), or Ni(II), were observed to result in substantial differences in affinity for hydrophobic guests in water. Changing the metal ion from iron(II) to cobalt(II) or nickel(II) increases the size of the interior cavity of the cage and allows encapsulation of larger guest molecules. NMR spectroscopy was used to study the recognition properties of the iron(II) and cobalt(II) cages towards small hydrophobic guests in water, and single-crystal X-ray diffraction was used to study the solid-state complexes of the iron(II) and nickel(II) cages.