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Issue 10, 2015
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Synthesis, crystal structures and magnetic properties of mer-cyanideiron(iii)-based 1D heterobimetallic cyanide-bridged chiral coordination polymers

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Abstract

Two pairs of cyanide-bridged Fe(III)–Mn(III)/Cu(II) chiral enantiomer coordination polymers {[Mn(S,S/R,R-Salcy)(CH3OH)2]{[Mn(S,S/R,R-Salcy)][Fe(bbp)(CN)3]}}2n (1,2) (bbp = bis(2-benzimidazolyl)pyridine dianion) and {[Cu(S,S/R,R-Chxn)2]2[Fe2(tbbp)(CN)6]}n (3,4) (tbbp = tetra(3-benzimidazolyl)-4,4′-bipyridine tetraanion) have been successfully prepared by employing mer-tricyanometallate [PPh4]2[Fe(bbp)(CN)3] or the newly bimetallic mer-cyanideiron(III) precursor K4[Fe2(tbbp)(CN)6] as building blocks and with chiral manganese(III)/copper(II) compounds as assemble segments. The four complexes have been characterized by elemental analysis, IR spectroscopy, circular dichroism (CD) and magnetic circular dichroism (MCD) spectra. Single X-ray diffraction reveals that complexes 1 and 2 possess a single anionic chain structure consisting of the asymmetric chiral {[Mn(S,S/R,R-Salcy)][Fe(bbp)(CN)3]}22− unit with free [Mn(S,S/R,R-Salcy)]+ as balanced cations. The cyanide-bridged Fe(III)–Cu(II) complexes 3 and 4 can be structurally characterized as neutral ladder-like double chains composed of the alternating cyanide-bridged Fe–Cu units. Our investigation of magnetic susceptibilities reveals the antiferromagnetic coupling between the cyanide-bridged Fe(III) and Mn(III)/Cu(II) ions for complexes 1–4. These results have been further confirmed by theoretical simulation through numerical matrix diagonalization techniques using a Fortran program or a uniform chain model, leading to the coupling constants J = −7.36 cm−1, D = −1.52 cm−1 (1) and J = −4.35 cm−1 (3), respectively.

Graphical abstract: Synthesis, crystal structures and magnetic properties of mer-cyanideiron(iii)-based 1D heterobimetallic cyanide-bridged chiral coordination polymers

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Article information


Submitted
23 Oct 2014
Accepted
22 Jan 2015
First published
26 Jan 2015

Dalton Trans., 2015,44, 4655-4664
Article type
Paper
Author version available

Synthesis, crystal structures and magnetic properties of mer-cyanideiron(III)-based 1D heterobimetallic cyanide-bridged chiral coordination polymers

D. Zhang, S. Zhuo, H. Zhang, P. Wang and J. Jiang, Dalton Trans., 2015, 44, 4655
DOI: 10.1039/C4DT03274H

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