Issue 12, 2015

Triazolate-based 3D frameworks and a 2D layer with centrosymmetric CuII7, CuII5, CuII4 clusters and tunable interlayer/interchain compactness: hydrothermal syntheses, crystal structures and magnetic properties

Abstract

Four 1,2,3-triazolate-based coordination polymers (CPs) with varied dimensionality, different nuclearity numbers and core topologies, [Cu4(μ-OH)(μ3-OH)(ta)2(btec)]n (1), {[Cu63-OH)2(ta)8(tp)]·2.5H2O}n (2), {[Cu53-OH)2(ta)4(ip)2]·2H2O}n (3) and {[Cu5(μ-OH)23-OH)2(ta)2(pa)2]·2H2O}n (4) (ta = 1,2,3-triazolate, btec = 1,2,4,5-benzenetetracarboxylate, tp = terephthalate, ip = isophthalate and pa = phthalate), were hydrothermally synthesized by varying the numbers and positions of the carboxylate group appended on the phenyl tether, and structurally and magnetically characterized. The former three entities are three-dimensional (3D) robust frameworks with a (44·62)(411·65)2(413·610·85) topological net containing centrosymmetric CuII7 clusters, square-planar CuII1 cores and tetratopic btec4− linkers for 1, a pillared-layered structure consisting of CuII5 + CuII1-based coplanar layers and ditopic tp2− pillars for 2 as well as a microporous architecture derived from CuII5 clusters and directional ip2− connectors for 3. In contrast, complex 4 exhibits an undulated two-dimensional (2D) layer with alternating CuII4 + CuII1 chains interconnected by anionic pa2− connectors. Crystallographically, the increment of the local nuclearity from CuII4 up to CuII7 in 1–4 benefits greatly from the synergistic co-coordination of the hydroxyl group and the coplanar ta ligand towards the metal ion, and the interlayer/interchain compactness is significantly tuned by the position isomerism of the dicarboxylate moieties. Due to the antiferromagnetic coupling in the local clusters and the asymmetric superexchange by μ3-ta mediator, these complexes exhibit different spin ground states (paramagnetic S = 1 and 1/2, ferrimagnetic S = 1/2 as well as spin canting) at low temperatures, which are informative for polynuclear-based magnetic materials.

Graphical abstract: Triazolate-based 3D frameworks and a 2D layer with centrosymmetric CuII7, CuII5, CuII4 clusters and tunable interlayer/interchain compactness: hydrothermal syntheses, crystal structures and magnetic properties

Supplementary files

Article information

Article type
Paper
Submitted
27 Dec 2014
Accepted
08 Feb 2015
First published
10 Feb 2015

Dalton Trans., 2015,44, 5826-5836

Author version available

Triazolate-based 3D frameworks and a 2D layer with centrosymmetric CuII7, CuII5, CuII4 clusters and tunable interlayer/interchain compactness: hydrothermal syntheses, crystal structures and magnetic properties

Y. Zhang, H. Zhao, E. Yang, Z. Liu, Q. Shang and X. Zhao, Dalton Trans., 2015, 44, 5826 DOI: 10.1039/C4DT04013A

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