Spin canting in an unprecedented three-dimensional pyrophosphate- and 2,2'-bipyrimidine-bridged cobalt(II) framework.

The three-dimensional cobalt(ii) compound of formula {[Co(2)(P(2)O(7))(bpym)(2)].12H(2)O}(n), where the pyrophosphate and 2,2'-bipyrimidine act as bridging ligands, is a new example of a spin-canted antiferromagnet with T(c) = 19 K.

Selective Guest Inclusion in Oxalate-Based Iron(III) Magnetic Coordination Polymers

The preparation and structural characterization of four novel oxalate-based iron(III) compounds of formulas {(MeNH3)2[Fe2(ox)2Cl4]·2.5H2O}n (1), K(MeNH3)[Fe(ox)Cl3(H2O)] (2), {MeNH3[Fe2(OH)(ox)2Cl2]·2H2O}n (3), and {(H3O)(MeNH3)[Fe2O(ox)2Cl2]·3H2O}n (4) (MeNH3+ = methylammonium cation and H2ox = oxalic acid) are reported here. 1 is an anionic waving chain of oxalato-bridged iron(III) ions with peripheral chloro ligands, the charge balance being ensured by methylammonium cations. 2 is a mononuclear complex with a bidentate oxalate, three terminal chloro ligands, and a coordinated water molecule achieving the six-coordination around each iron(III) ion. Its negative charge is balanced by potas…

A Copper(II)-Cytidine Complex as a Building Unit for the Construction of an Unusual Three-Dimensional Coordination Polymer

The chiral [Cu(cyd) 4 ] 6- anion acts as a multiarmed complex-ligand toward auxiliary copper(II) centers leading to the first example of cytidinate-bridged three-dimensional (3D) coordination polymer of formula [Cu 6 (H 2 O) 7 (ClO 4 ) 3 Cu(cyd) 4 ]-(ClO 4 ) 3 (1). Single crystal X-ray analysis of 1 shows a unique 3D covalent network supported by the exclusive hypercoordination of the cytidinate ligand that bridges four crystallographically independent copper(II) ions via the N3, O2, O2', O3', and O5' set of atoms. Magnetic susceptibility measurements in the temperature range 1.9-295 K reveal the coexistence of ferro- and antiferromagnetic interactions within the hexacopper(II) core of 1, t…

Synthesis and Enhanced Capture Properties of a New BioMOF@SWCNT‐BP: Recovery of the Endangered Rare‐Earth Elements from Aqueous Systems (Adv. Mater. Interfaces 16/2021)

Enhancing the Magnetic Coupling of Oxalato-Bridged ReIV2MII (M = Mn, Co, Ni, and Cu) Trinuclear Complexes via Peripheral Halide Ligand Effects

Four heterotrinuclear Re(IV)(2)M(II) compounds of general formula (NBu(4))(2)[{Re(IV)Br(4)(μ-ox)}(2)M(II)(Him)(2)] [NBu(4)(+) = tetra-n-butylammonium cation, ox = oxalate, Him = imidazole; M = Mn (1), Co (2), Ni (3), and Cu (4)] have been synthesized by using the novel mononuclear complex [Re(IV)Br(4)(ox)](2-) as a ligand toward divalent first-row transition metal ions in the presence of imidazole. Compounds 1-4 are isostructural complexes whose structure contains discrete trinuclear [{Re(IV)Br(4)(μ-ox)}(2)M(II)(Him)(2)](2-) anions and bulky NBu(4)(+) cations. The Re and M atoms are six-coordinated: four peripheral bromo and two oxalate-oxygens (at Re), and two cis-coordinated imidazole mol…

Reverse osmosis and nanofiltration membranes for highly efficient PFASs removal: overview, challenges and future perspectives

Today, it is extremely urgent to face the increasing shortage of clean and safe water resources, determined by the exponential growth of both world population and its consumerism, climate change and pollution. Water remediation from traditional chemicals and contaminants of emerging concerns (CECs) is supposed to be among the major methods to solve water scarcity issues. Reverse osmosis (RO) and nanofiltration (NF) membrane separation technologies have proven to be feasible, sustainable and highly effective methods for the removal of contaminants, comprising the extremely persistent and recalcitrant perfluoroalkyl substances (PFASs), which failed to be treated through the traditional water …

Highly Anisotropic Rhenium(IV) Complexes: New Examples of Mononuclear Single-Molecule Magnets

The rhenium(IV) complex (NBu4)2[ReBr4(ox)] (1) (ox = oxalate and NBu4(+) = tetra-n-butylammonium cation) has been prepared and its crystal structure determined by X-ray diffraction. The structure is made up of discrete [ReBr4(ox)](2-) anions and bulky NBu4(+) cations. Each [ReBr4(ox)](2-) anion is surrounded by six NBu4(+) cations, which preclude any significant intermolecular contact between the anionic entities, the shortest rhenium···rhenium distance being 9.373(1) Å. Variable temperature dc and ac magnetic susceptibility measurements and field-dependent magnetization experiments on polycrystalline samples of 1 reveal the occurrence of highly anisotropic magnetically isolated Re(IV) cent…

Guanine-containing copper(ii) complexes: synthesis, X-ray structures and magnetic properties

Three new compounds of formula {[Cu(gua)(H(2)O)(3)](BF(4))(SiF(6))(1/2)}(n) (1), {[Cu(gua)(H(2)O)(3)](CF(3)SO(3))(2).H(2)O}(n) (2) and [Cu(gua)(2)(H(2)O)(HCOO)]ClO(4).H(2)O.1/2HCOOH] (3) [gua = 2-amino-1H-purin-6(9H)-one] showing the unprecedented coordination of neutral guanine, have been synthesised and structurally characterized. The structures of the compounds 1 and 2 contain uniform copper(II) chains of formula [Cu(gua)(H(2)O)(3)](n)(2n+), where the copper atoms are bridged by guanine ligands coordinated via N(3) and N(7). The electroneutrality is achieved by uncoordinated tetrafluoroborate and hexafluorosilicate (1) and triflate (2). Each copper atom in 1 and 2 is five-coordinated in …

Synthesis of a rod-based porous coordination polymer from a nucleotide as a sequential chiral inductor

We report the two-step synthesis of a novel chiral rod-based porous coordination polymer (PCP). The chemical approach consists of the use of a previously prepared bis(ethylenediamine) copper monomer [Cu(en)]2(NO3)2 [where en = ethylenediamine] reacting with the cytidine 5′-monophosphate (CMP) nucleotide. The bis(ethylenediamine) copper compound—stabilized by axial coordination of nitrate counter-anions—reacts in the presence of sodium salt of CMP to yield right-handed copper(II) chains of P helicity with formula [Cu2(en)2(CMP)2]·5H2O (1). The axial coordination of the CMP2- ligands through the N3 and O2 sites (free nitrogen and carbonyl groups) of the cytosine nucleobase and oxygen atoms of…

A novel supramolecular assembly in an iron(III) compound exhibiting magnetic ordering at 70 K

Ethyl-substituted ammonium cation allows the preparation of an unprecedented oxo- and oxalato-bridged supramolecular three-dimensional network. The compound exhibits magnetic ordering with Tc = 70 K due to a weak spin canting. Julve Olcina, Miguel, Miguel.Julve@uv.es ; Lloret Pastor, Francisco, Francisco.Lloret@uv.es

Synthesis and Enhanced Capture Properties of a New BioMOF@SWCNT‐BP: Recovery of the Endangered Rare‐Earth Elements from Aqueous Systems

The Cation as a Tool to Get Spin-Canted Three-Dimensional Iron(III) Networks

Alkyl-substituted ammonium cations (X) allow the preparation of a series of spin-canted oxo- and oxalato-bridged three-dimensional iron(III) networks, exhibiting magnetic ordering at T(c) values ranging from 40 to 56 K. The value of T(c) varies with the cation despite the lack of significant structural modifications.

Cubane-Type CuII4 and MnII2MnIII2 Complexes Based on Pyridoxine: A Versatile Ligand for Metal Assembling

By using Vitamin B6 in its monodeprotonated pyridoxine form (PN-H) [PN = 3-hydroxy-4,5-bis(hydroxymethyl)-2-methylpyridine], two tetranuclear compounds of formula [Mn4(PN-H)4(CH3CO2)3Cl2]Cl·2CH3OH·2H2O (1) and [Cu4(PN-H)4Cl2(H2O)2]Cl2 (2) have been synthesized and magneto-structurally characterized. 1 crystallizes in the triclinic system with space group P1 whereas 2 crystallizes in the orthorhombic system with Fdd2 as space group. They exhibit Mn(II)2Mn(III)2 (1) and Cu(II)4 (2) cubane cores containing four monodeprotonated pyridoxine groups simultaneously acting as chelating and bridging ligands (1 and 2), three bridging acetate ligands in the syn-syn conformation (1), and two terminally …

Self-Assembled One- and Two-Dimensional Networks Based on NH2Me2[ReX5(DMF)] (X = Cl and Br) Species: Polymorphism and Supramolecular Isomerism in Re(IV) Compounds

Three mononuclear rhenium(IV) compounds of general formula NH 2 Me 2 [ReX 5 (DMF)] [NH 2 Me 2 + = dimethylammonium cation, DMF = N,N-dimethylformamide, and X = Cl (1 and 2) and Br (3)] have been prepared and characterized. In all three cases, the rhenium atom is six-coordinated by five chloro (1 and 2) or bromo (3) atoms and one oxygen atom from a DMF molecule (1―3) building a somewhat distorted octahedral surrounding. Short Re IV ―X · · · X―Re IV contacts and H-bonds occur in the crystal lattice generating novel supramolecular Re(IV) architectures. 1 and 2 are polymorphs and supramolecular isomers that exhibit supramolecular ladder-like ( 1 ) and rectangular two-dimensional grids (2), the …

Triorganotin(IV) derivatives of 7-amino-2-(methylthio)[1,2,4]triazolo[1,5-a]pyrimidine-6-carboxylic acid. Synthesis, spectroscopic characterization, in vitro antimicrobial activity and X-ray crystallography

Triorganotin(IV) complexes of the 7-amino-2-(methylthio)[1,2,4]triazolo[1,5-a]pyrimidine-6-carboxylic acid (HL), Me 3 SnL(H 2 O), ( 1 ), [ n -Bu 3 SnL] 2 (H 2 O), ( 2 ), Ph 3 SnL(MeOH), ( 3 ), were synthesized by reacting the amino acid with organotin(IV) hydroxides or oxides in refluxing methanol. The complexes have been characterized by elemental analysis, 1 H, 13 C and 119 Sn NMR, IR, Raman and 119 Sn Mossbauer spectroscopic techniques. Single crystal X-ray diffraction data were obtained for compounds ( 2 ) and ( 3 ). Ph 3 SnL(MeOH) presents a trigonal bipyramidal structure with the organic groups on the equatorial plane and the axial positions occupied by a ligand molecule, coordinated …

Anion-Directed Self-Assembly of Unusual Discrete and One-Dimensional Copper(II) Complexes of 3,6-Bis(2′-pyridyl)pyridazine

The preparation and crystal structures of six new copper(II) compounds of formula [Cu(dppn)2(ClO4)]ClO4 (1), [Cu2(dppn)(OH)(ClO4)3(H2O)3]·H2O (2), [Cu2(dppn)2(H2O)2](ClO4)4 (3), [Cu2(dppn)2(ClO4)4] (4), {[Cu2(dppn)(N3)4]·H2O/[Cu2(dppn)(N3)4(H2O)]}n (5) and {[Cu2(dppn)(OH)(dca)3]·H2O}n (6) [dppn = 3,6-bis(2′-pyridyl)pyridazine and dca = dicyanamide] are reported. 1 is a mononuclear complex where two bidentate dppn molecules and a monodentate perchlorate build an intermediate square pyramidal/trigonal bipyramidal (sp/tbp) five-coordinate environment around the copper(II) ion, the overall positive charge being balanced by a free perchlorate anion. 2–4 are dinuclear complexes with either one (2…

CCDC 1495414: Experimental Crystal Structure Determination

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CCDC 2051219: Experimental Crystal Structure Determination

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CCDC 1495415: Experimental Crystal Structure Determination

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CCDC 1495416: Experimental Crystal Structure Determination

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CCDC 1495417: Experimental Crystal Structure Determination

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CCDC 854108: Experimental Crystal Structure Determination

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