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

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 47; no. 40; pp. 14327 - 14339
• Main Authors: Gu, Jin-Zhong, Cai, Yan, Wen, Min, Shi, Zi-Fa, Kirillov, Alexander M.
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 2018
• Subjects: Absorption spectra; Benzoic acid; Cadmium; Catalysis; Coordination compounds; Coordination polymers; Crystallization; Crystallography; Emission analysis; Materials selection; Metal-organic frameworks; Methylene blue; Photocatalysis; Photodegradation; Porosity; Reflectance; Single crystals; Terephthalic acid; Topology; Ultraviolet radiation; X-ray diffraction
• ISSN: 1477-9226; 1477-9234; 1477-9234
• DOI: 10.1039/C8DT02467G

Two multifunctional, ether-bridged tricarboxylic acids, 2-(4-carboxylphenoxy)terephthalic acid (H 3 cpta) and 2-(3,5-dicarboxylatobenzyloxy)benzoic acid (H 3 dbba), 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 ), {[Cd 3 (μ 5 -cpta) 2 (phen) 3 ]·8H 2 O} n ( 2 ), {[Cd 3 (μ 5 -cpta) 2 (2,2′-bipy) 3 ]·6H 2 O} n ( 3 ), {[Cd(μ 3 -cpta)(Hbpa)]·2H 2 O} n ( 4 ), {[Cd 6 (μ 4 -cpta) 2 (μ 6 -cpta) 2 (H 2 biim) 2 (H 2 O) 6 ]·5H 2 O} n ( 5 ), [Cd 3 (μ 4 -cpta) 2 (μ-prz)(H 2 O) 4 ] n ( 6 ), {[Cd 3 (μ 4 -dbba) 2 (phen) 3 ]·H 2 O} n ( 7 ), and {[Cd 3 (μ 3 -dbba) 2 (2,2′-bipy) 3 (H 2 O) 3 ]·2H 2 O} 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 (H 2 biim), 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 (10 3 )-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 H 3 dbba.