Four New Three-Dimensional Polyoxometalate-Based Metal?Organic Frameworks Constructed From [Mo6O18(O3AsPh)2]4? Polyoxoanions and Copper(I)-Organic Fragments: Syntheses, Structures, Electrochemistry, and Photocatalysis Properties

摘要

Four novel polyoxometalate-based copper(I)-norganic frameworks, namely, [CuIn2(cis-L1)2][CuIn2(trans-nL1)2Mo6O18(O3AsPh)2] (1), [CuIn4(L2)4Mo6O18(O3AsPh)2]n( 2 ) , [CuIn4(L3)4Mo6O1 8(O3AsPh)2] (3 ) , andn[CuIn4(L4)2Mo6O18(O3AsPh)2] (4) (L1 = 1,3-bis(1,2,4-triazol-n1-yl)propane, L2 = 1,4-bis(1,2,4-triazol-1-yl)butane, L3 =n1,5-bis(1,2,4-triazol-1-yl)pentane, and L4 = 1,6-bis(1,2,4-ntriazol-1-yl)hexane), have been successfully synthesized undernhydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and furtherncharacterized by elemental analyses, infrared spectra (IR), UV−vis spectra, powder X-ray diffraction (PXRD), andnthermogravimetric (TG) analyses. Compound 1 is composed of two crystallographically independent and distinct polymericnmotifs: one-dimensional (1D) S-shaped chain and two-dimensional (2D) undulated layer. The S-shaped chains penetrated intonthe 2D parallel layers to generate an unusual 1D + 2D → three-dimensional (3D) polypseudo-rotaxane framework. In 2, thenAs2Mo6 polyoxoanions in tetradentate modes link four neighboring −L2−Cu−L2− chains to produce a rare 3D trinodal (3,4)-nconnected self-penetrated framework with Point Symbol of (83)2(82·124). In 3, adjacent CuI atoms are linked by As2Mo6npolyoxoanions and L3 ligands into a 2D layer. The layers are further interlocked by the two nearest neighboring ones to form an3D polycatenated framework. In 4, L4 ligands bridge four CuI atoms to yield 2D wavelike layers, which are further linked by thenoctadentate As2Mo6 polyoxoanions to form a 3D tetranodal (3,4,6)-connected framework with Point Symbol ofn(63)(4·63·82)(64·82)(42·62·810·10). In addition, the photocatalytic activities of compounds 1, 3, and 4 for decomposition ofnmethylene blue (MB) under UV light have been investigated. Moreover, their electrochemical properties have also been studiednin 1 M H2SO4 aqueous solution.