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Abstract: Two new metal–organic frameworks based on cyclic-type dodecanuclear copper units, (Me4N)6[Cu12(OMe)6(pz)6(BTC)6]·18H2O 1 and (Me4N)6[Cu12(OH)6(pz)6(BTC)6]·21H2O 2 (pz=pyrazolate, BTC=1,3,5-benzenetricarboxylate), have been prepared by the solvothermal reactions of copper salts, Hpz and H3BTC ligands. The cyclic-type Cu12 unit in 1 and 2 is constructed by twelve CuII ions linked together by μ2-OH or μ2-OMe and unidentate carboxylate groups at the inner- and μ-pz and bidentate carboxylate groups at the outer surface of the toroid. In 1 and 2, each Cu12 unit is connected to 12 other units by BTC linkers, leading to 12-connected three-dimensional porous frameworks. The photocatalytic investigations indicate that compounds 1 and 2 exhibit photocatalytic activity for the degradation of RhB. [Copyright &y& Elsevier]

Abstract: A new metal–organic framework based on hexanuclear copper units, Cu6(μ3-O)(μ3-OH)(pz)6(btc) (pz=pyrazolate, btc=1,3,5-benzenetricarboxylate) 1, has been prepared by the hydrothermal reaction of Cu2+ ions, Hpz and H3btc ligands in a methanolic solution. The hexanuclear copper building unit in 1 is composed of two triangular Cu3O(H)(pz)3 units bridged by carboxyl groups, in which each Cu center is coordinatively unsaturated with open coordination sites. The photocatalytic investigation indicates that compound 1 exhibits a higher photocatalytic activity for the degradation of Rhodamine B. [Copyright &y& Elsevier]