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Construction of (3,8)‐connected three‐dimensional cobalt(II) and copper(II) coordination polymers with 1,3‐bis[(1,2,4‐triazol‐4‐yl)methyl]benzene and benzene‐1,3,5‐tricarboxylate ligands
Authors:Ya-Qian Zhang  Vladislav A Blatov  Xiu-Xiu Lv  Ding-Yi Tang  Lin-Lu Qian  Ke Li  Bao-Long Li
Abstract:Coordination polymers (CPs) have been widely studied because of their diverse and adjustable topologies and wide‐ranging applications in luminescence, chemical sensors, magnetism, photocatalysis, gas adsorption and separation. In the present work, two coordination polymers, namely poly(μ5‐benzene‐1,3,5‐tricarboxylato‐κ6O1:O1′:O3:O3:O5,O5′){μ3‐1,3‐bis(1,2,4‐triazol‐4‐yl)methyl]benzene‐κ3N:N′:N′′}di‐μ3‐hydroxido‐dicobalt(II)], Co2(C9H3O6)(OH)(C12H12N6)]n or Co2(btc)(OH)(mtrb)]n, (1), and polydiaquabis(μ3‐benzene‐1,3,5‐tricarboxylato‐κ3O1:O3:O5)bis{μ3‐1,3‐bis(1,2,4‐triazol‐4‐yl)methyl]benzene‐κ3N:N′:N′′}tetra‐μ3‐hydroxido‐tetracopper(II)] monohydrate], {Cu4(C9H3O6)2(OH)2(C12H12N6)2(H2O)2]·H2O}n or {Cu4(btc)2(OH)2(mtrb)2(H2O)2]·H2O}n, (2), were synthesized by the hydrothermal method using 1,3‐bis(1,2,4‐triazol‐4‐yl)methyl]benzene (mtrb) and benzene‐1,3,5‐tricarboxylate (btc3?). CP (1) exhibits a (3,8)‐coordinated three‐dimensional (3D) network of the 3,8T38 topological type, with a point symbol of {4,5,6}2{42·56·616·72·82}, based on the tetranuclear hydroxide cobalt(II) cluster Co43‐OH)2]. CP (2) shows a (3,8)‐coordinated tfz‐d topology, with a point symbol of {43}2{46·618·84}, based on the tetranuclear hydroxide copper(II) cluster Cu43‐OH)2]. The different (3,8)‐coordinated 3D networks based on tetranuclear hydroxide–metal clusters of (1) and (2) are controlled by the different central metal ions CoII for (1) and CuII for (2)]. The thermal stabilities and solid‐state optical diffuse‐reflection spectra were measured. The energy band gaps (Eg) obtained for (1) and (2) were 2.72 and 2.29 eV, respectively. CPs (1) and (2) exhibit good photocatalytic degradation of the organic dyes methylene blue (MB) and rhodamine B (RhB) under visible‐light irradiation.
Keywords:topological analysis  three‐dimensional coordination polymer  (3  8)‐connected network  crystal structure  tetranuclear hydroxide cobalt(II) cluster  tetranuclear hydroxide copper(II) cluster  thermal stability  photocatalytic degradation  1  3‐bis[(1  2  4‐triazol‐4‐yl)methyl]benzene  benzene‐1  3  5‐tricarboxylate  methylene blue  rhodamine B
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