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Issue 11, 2019
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Dimensionality controlled by light exposure: 1D versus 3D oxalate-bridged [CuFe] coordination polymers based on an [Fe(C2O4)3]3− metallotecton

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Abstract

Heterodimetallic [CuIIFeIII] one-dimensional (1D) coordination polymers {NH4[{Cu(bpy)}2(C2O4)Fe(C2O4)3]·H2O}n (1) and {K[{Cu(bpy)}2(C2O4)Fe(C2O4)3]·H2O}n (2) (bpy = 2,2′-bipyridine) were obtained using a building block approach by a layering technique, from the reaction of an aqueous solution of [Fe(C2O4)3]3− and methanol solutions containing Cu2+ and bpy. In a test tube without the presence of light, partial decomposition of the tris(oxalato)ferrate(III) anion occurred yielding oxalate-bridged dinuclear [Cu(bpy)(C2O4)Cu(bpy)]2+ units. These cationic species are mutually connected through oxalate groups from [Fe(C2O4)3]3−, thus forming ladder-like topologies in compounds 1 and 2. When the same reaction mixture was exposed to daylight, initial building block [Fe(C2O4)3]3− undergoes photoreduction producing [CuIIFeII] three-dimensional (3D) coordination polymer {[Cu(bpy)3][Fe2(C2O4)3]·H2O}n (3a). In addition, under hydrothermal conditions, the same reduction occurs giving compound {[Cu(bpy)3][Fe2(C2O4)3]}n (3b) that crystallizes without the water molecule. The molecular structure of 3a and 3b consists of a 3D anionic network {[Fe2(C2O4)3]}n2n and tris-chelated cations [Cu(bpy)3]2+ occupying the vacancies in the framework. Very strong antiferromagnetic coupling between two copper(II) ions from [Cu(bpy)(C2O4)Cu(bpy)]2+ species transferred through the oxalate bridge was determined in 1 and 2 from the magnetization measurements. In 3a and 3b, strong exchange interaction is present in the Fe-oxalate network, {[Fe2(C2O4)3]}n2n, and the ground state of the compounds tends to zero-magnetization at the lowest temperature.

Graphical abstract: Dimensionality controlled by light exposure: 1D versus 3D oxalate-bridged [CuFe] coordination polymers based on an [Fe(C2O4)3]3− metallotecton

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Supplementary files

Article information


Submitted
25 Jul 2019
Accepted
24 Sep 2019
First published
25 Sep 2019

Inorg. Chem. Front., 2019,6, 3327-3335
Article type
Research Article

Dimensionality controlled by light exposure: 1D versus 3D oxalate-bridged [CuFe] coordination polymers based on an [Fe(C2O4)3]3− metallotecton

L. Kanižaj, L. Androš Dubraja, F. Torić, D. Pajić, K. Molčanov, E. Wenger and M. Jurić, Inorg. Chem. Front., 2019, 6, 3327
DOI: 10.1039/C9QI00926D

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