Issue 5, 2013

Syntheses, structures, photoluminescence, photocatalysis, and photoelectronic effects of 3D mixed high-connected metal–organic frameworks based on octanuclear and dodecanuclear secondary building units

Abstract

Four novel metal–organic frameworks (MOFs) based on high-nuclear metal carboxylate clusters, namely, [Zn4(L)23-OH)2(H2O)1.5]·2H2O (1), [Zn5Na(L)23-OH)4(CH3CH2O)(H2O)2] (2), [Cd4(L)2(BIME)0.53-OH)2(H2O)1.5]·2H2O (3), and [Zn4(L)2(BET)0.53-OH)2(H2O)] (4), where H3L = (3,5-dicarboxyl-phenyl)-(4-(2′-carboxyl-phenyl)-benzyl)ether, BET = 1,1′-(2′-oxybis(ethane-2,1-diyl))bis(1,2,4-triazol-1-yl), BIME = 1,2-bis(imidazol-1-yl)ethane, have been synthesized under hydrothermal conditions. In 1, each planar octanuclear zinc cluster [Zn83-OH)8(CO2)12(H2O)3] is linked by twelve L anions to give an unusual (3,12)-connected framework with (43)2(420·628·818) topology. In 2, dodecanuclear heterometallic clusters [Zn10Na23-OH)8(CO2)12(CH3CH2O)2(H2O)4] are surrounded by twelve L anions to form a (3,12)-connected net with the same topology as 1. However, 3 exhibits a rare (3,14)-connected (43)(324)(34·420·514·634·711·88) net based on octanuclear cadmium cluster [Cd8(BIME)23-OH)4(CO2)12(H2O)4]·2H2O as a 14-connected node and H3L as a 3-connected node. In 4, each octanuclear zinc cluster [Zn8(BET)23-OH)4(CO2)12(H2O)2] is linked by twelve L anions to furnish a (3,14)-connected net with the same topology as 3. The optical energy gaps and photoluminescence were investigated for the compounds. Moreover, compounds 1–4 exhibit good photocatalytic activities for degradation of methylene blue (MB) under UV irradiation and show good stability towards UV photocatalysis. In addition, 1 and 4 display a photocurrent density under several on–off cycles of illumination.

Graphical abstract: Syntheses, structures, photoluminescence, photocatalysis, and photoelectronic effects of 3D mixed high-connected metal–organic frameworks based on octanuclear and dodecanuclear secondary building units

Supplementary files

Article information

Article type
Paper
Submitted
28 Aug 2012
Accepted
22 Oct 2012
First published
09 Nov 2012

Dalton Trans., 2013,42, 1567-1580

Syntheses, structures, photoluminescence, photocatalysis, and photoelectronic effects of 3D mixed high-connected metal–organic frameworks based on octanuclear and dodecanuclear secondary building units

P. Du, Y. Yang, J. Yang, B. Liu and J. Ma, Dalton Trans., 2013, 42, 1567 DOI: 10.1039/C2DT31964K

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