Issue 40, 2018

A new series of Cd(ii) metal–organic architectures driven by soft ether-bridged tricarboxylate spacers: synthesis, structural and topological versatility, and photocatalytic properties

Abstract

Two multifunctional, ether-bridged tricarboxylic acids, 2-(4-carboxylphenoxy)terephthalic acid (H3cpta) and 2-(3,5-dicarboxylatobenzyloxy)benzoic acid (H3dbba), were used as unexplored and highly versatile building blocks for the hydrothermal generation of a novel series of cadmium(II) metal–organic architectures. These were formulated as [Cd(μ-Hcpta)(phen)(py)]n (1), {[Cd35-cpta)2(phen)3]·8H2O}n (2), {[Cd35-cpta)2(2,2′-bipy)3]·6H2O}n (3), {[Cd(μ3-cpta)(Hbpa)]·2H2O}n (4), {[Cd64-cpta)26-cpta)2(H2biim)2(H2O)6]·5H2O}n (5), [Cd34-cpta)2(μ-prz)(H2O)4]n (6), {[Cd34-dbba)2(phen)3]·H2O}n (7), and {[Cd33-dbba)2(2,2′-bipy)3(H2O)3]·2H2O}n (8) on the basis of single-crystal X-ray diffraction, elemental analysis, FTIR, PXRD, and TGA data. Products 1–8 were assembled in the presence of N-donor crystallization mediators selected from pyridine (py), 1,10-phenanthroline (phen), 2,2′-bipyridine (2,2′-bipy), bis(4-pyridyl)amine (bpa), 2,2′-biimidazole (H2biim), or piperazine (prz). The nature of the crystallization mediator and/or the type of principal tricarboxylate building block have a significant effect on the structural diversity, dimensionality, and topology of the resulting cadmium-organic architectures. These span from 1D (1, 8) and 2D (7) coordination polymers to 3D metal–organic frameworks (2–6) with intricate topologies (3,4,5T64 in 2 and 3, utp (103)-d in 4, 3,4,4T9 in 6) that also include unprecedented types in 5 and 7. Besides, MOF 6 features a 3D + 3D two-fold interpenetrated framework. Luminescent and photocatalytic properties of selected materials were investigated, showing that coordination polymer 7 is a promising photocatalyst for the UV-light-driven degradation of methylene blue as a model organic dye pollutant. Moreover, products 7 and 8 are the first examples of structurally characterized coordination compounds derived from H3dbba.

Graphical abstract: A new series of Cd(ii) metal–organic architectures driven by soft ether-bridged tricarboxylate spacers: synthesis, structural and topological versatility, and photocatalytic properties

Supplementary files

Article information

Article type
Paper
Submitted
18 juin 2018
Accepted
17 août 2018
First published
21 août 2018

Dalton Trans., 2018,47, 14327-14339

A new series of Cd(II) metal–organic architectures driven by soft ether-bridged tricarboxylate spacers: synthesis, structural and topological versatility, and photocatalytic properties

J. Gu, Y. Cai, M. Wen, Z. Shi and A. M. Kirillov, Dalton Trans., 2018, 47, 14327 DOI: 10.1039/C8DT02467G

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