Jump to main content
Jump to site search


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

Author affiliations

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 25 Jul 2019, accepted on 24 Sep 2019 and first published on 25 Sep 2019


Article type: Research Article
DOI: 10.1039/C9QI00926D
Inorg. Chem. Front., 2019, Advance Article

  •   Request permissions

    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, Advance Article , DOI: 10.1039/C9QI00926D

Search articles by author

Spotlight

Advertisements