Rational design of a new class of heterobimetallic molecule-based magnets: Synthesis, crystal structures, and magnetic properties of oxamato-bridged (M′=LiI and MnII; M=NiII and CoII) open-frameworks with a three-dimensional honeycomb architecture

Abstract Two new series of oxamato-bridged heterobimetallic coordination networks of general formula Li5[Li3M2(mpba)3(H2O)6] · 31H2O [M = NiII (1a) and CoII (1b)] and Li2[Mn3M2(mpba)3(H2O)6] · 22H2O [M = NiII (2a) and CoII (2b)] have been prepared from the metal-mediated self-assembly of the hexakis(bidentate), triple-stranded dinickel(II) and dicobalt(II) complexes [M2(mpba)3]8− [mpba = meta-phenylenebis(oxamato)] with either monovalent lithium(I) or divalent manganese(II) ions respectively, in water. X-ray structural analyses of 1a and 1b show an anionic three-dimensional network formed by an infinite parallel array of oxamato-bridged Li 3 I M 2 II (M = Ni and Co) hexagonal layers, which …

Porous Coordination Polymer Based on Bipyridinium Carboxylate Linkers with High and Reversible Ammonia Uptake

The zwitterionic bipyridinium carboxylate ligand 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium (pc1) in the presence of cadmium chloride affords novel porous coordination polymers (PCPs): [Cd4(pc1)3Cl6]·CdCl4·guest (1) crystallizing in the P3̅1c space group. In the structure, [Cd4Cl6(CO2)6] building units are linked together by six pc1 ligands, leading to a 3D high-symmetrical network exhibiting hexagonal channels along the c axis. The walls of this PCP consist of cationic electron-acceptor bipyridinium units. The PCP 1 reversibly adsorbs H2O and CH3OH up to about 0.1 g/g at saturation showing the adsorption isotherms characteristic of a moderately hydrophilic sorbent. Adsorption of ammonia (…

Supramolecular coordination chemistry of aromatic polyoxalamide ligands: A metallosupramolecular approach toward functional magnetic materials

Abstract The impressive potential of the metallosupramolecular approach in designing new functional magnetic materials constitutes a great scientific challenge for the chemical research community that requires an interdisciplinary collaboration. New fundamental concepts and future applications in nanoscience and nanotechnology will emerge from the study of magnetism as a supramolecular function in metallosupramolecular chemistry. Our recent work on the rich supramolecular coordination chemistry of a novel family of aromatic polyoxalamide (APOXA) ligands with first-row transition metal ions has allowed us to move one step further in the rational design of metallosupramolecular assemblies of …

Oligo-m-phenyleneoxalamide Copper(II) Mesocates as Electro-Switchable Ferromagnetic Metal–Organic Wires

Double-stranded copper(II) string complexes of varying nuclearity, from di- to tetranuclear species, have been prepared by the CuII-mediated self-assembly of a novel family of linear homo- and heteropolytopic ligands that contain two outer oxamato and either zero (1 b), one (2 b), or two (3 b) inner oxamidato donor groups separated by rigid 2-methyl-1,3-phenylene spacers. The X-ray crystal structures of these CuIIn complexes (n=2 (1 d), 3 (2 d), and 4 (3 d)) show a linear array of metal atoms with an overall twisted coordination geometry for both the outer CuN2O2 and inner CuN4 chromophores. Two such nonplanar all-syn bridging ligands 1 b–3 b in an anti arrangement clamp around the metal ce…

Variation of the ground spin state in homo- and hetero-octanuclear copper(II) and nickel(II) double-star complexes with a meso-helicate-type metallacryptand core.

Homo- and heterometallic octanuclear complexes of formula Na₂{[Cu₂(mpba)₃][Cu(Me₅dien)]₆}-(ClO₄)₆·12H₂O (1), Na₂{[Cu₂(Mempba)₃][Cu(Me₅dien)]₆}(ClO₄)₆·12H₂O (2), Na₂{[Ni₂(mpba)₃]-[Cu(Me₅dien)]₆}(ClO₄)₆·12H₂O (3), Na₂{[Ni₂(Mempba)₃][Cu(Me₅dien)]₆}(ClO₄)₆·9H₂O (4), {[Ni₂(mpba)₃][Ni(dipn)(H₂O)]₆}(ClO₄)₄·12.5H₂O (5), and {[Ni₂(Mempba)₃][Ni(dipn)-(H₂O)]₆}(ClO₄)₄·12H₂O (6) [mpba = 1,3-phenylenebis(oxamate), Mempba = 4-methyl-1,3-phenylenebis(oxamate), Me₅dien = N,N,N',N'',N''-pentamethyldiethylenetriamine, and dipn = dipropylenetriamine] have been synthesized through the "complex-as-ligand/complex-as-metal" strategy. Single-crystal X-ray diffraction analyses of 1, 3, and 5 show cationic M(II)₂M'(I…

Self-assembly, metal binding ability, and magnetic properties of dinickel(II) and dicobalt(II) triple mesocates

Two metallacyclic complexes of general formula Na-8[(M2L3)-L-II]center dot xH(2)O [M = Ni (4) and Co (5) with x = 15 (4) and 17 (5)] have been self-assembled in aqueous solution from N,N'-1,3-phenylenebis(oxamic acid) (H4L) and M2+ ions in a ligand/metal molar ratio of 3 : 2 in the presence of NaOH acting as base. X-Ray structural analyses of 4 and 5 show triple-stranded, dinuclear anions of the meso-helicate-type (so-called mesocates) with C-3h molecular symmetry. The two octahedral metal-tris(oxamate) moieties of opposite chiralities (Delta, Lambda form) are connected by three m-phenylene spacers at intermetallic distances of 6.822(2) (4) and 6.868(2) angstrom (5) to give a metallacryptan…

Tuning the Spin Ground State in Heterononanuclear Nickel(II)−Copper(II) Cylinders with a Triangular Metallacyclophane Core

3 páginas, 2 figuras, 1 gráfico.-- et al.

Inside Cover: Oligo-m-phenyleneoxalamide Copper(II) Mesocates as Electro-Switchable Ferromagnetic Metal-Organic Wires (Chem. Eur. J. 43/2010)

A Metallacryptand-Based Manganese(II)–Cobalt(II) Ferrimagnet with a Three-Dimensional Honeycomb Open-Framework Architecture

CCDC 1571877: Experimental Crystal Structure Determination

Related Article: Antonin Leblanc, Nicolas Mercier, Magali Allain, Marie-Claire Dul, Guy Weber, Nicolas Geoffroy, Jean-Pierre Bellat, Igor Bezverkhyy|2017|Dalton Trans.|46|15666|doi:10.1039/C7DT03541A

CCDC 1473082: Experimental Crystal Structure Determination

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