Ligand-induced isomerization: from 3D to 2D→3D POMOFs constructed from silicotungstate anions, Cu(i) and 1, n-di(4H-1, 2, 4-triazol-4-yl)benzene (n = 3, 4) ligands. Issue 34 (21st July 2016)

• Record Type: Journal Article
• Authors: Chen, Yan-Mei; Yu, Ying-Hui; Zhang, Han-Zhong; Hou, Guang-Feng; Gao, Jin-Sheng; Yan, Peng-Fei
• Is Part Of: CrystEngComm. Volume 18:Issue 34(2016)
• Page Start: 6389
• Page End: 6395
• Publication Date: 2016-07-21
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/c6ce01174h
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : Two novel POMOFs show ligand-induced isomerisation and photocatalytic activities towards the degradation of Rhodamine-B without other oxidants. Abstract : Two novel POMOFs, [Cu4 (1, 3-dtzb)4 (SiW12 O40 )] n (1 ) and [Cu4 (1, 4-dtzb)4 (SiW12 O40 )] n (2 ), based on Keggin-type polyoxometalates have been hydrothermally synthesized by altering organic ligands {1, n -di(4H-1, 2, 4-triazol-4-yl)benzene: n = 3 (1, 3-dtzb) and 4 (1, 4-dtzb)}. In POMOF1 constructed from the V-shaped 1, 3-dtzb meta -ligand, the ligands link the Cu(i ) ions to form a 20-member metallomacrocycle with [Cu2 (1, 3-dtzb)2 ] as the SBU, four of which assemble into a cage-like [Cu2 (1, 3-dtzb)2 ]4 motif to embed the POM anion, resulting in a 3D POMOF showing a new type of topological structure with a point symbol of {4·5 3 ·7 2 }{5 2 ·8}. However, when the ligand is changed to the 1, 4-dtzb straight para -ligand, POMOF2 with a different structure is achieved. The ligands link the Cu(i ) ions into a basic 3, 3-connected net, and then the POM anions insert into the space between two adjacent nets to form a POM-pillared double-layer framework. The large cavities of the POM-pillared double layers allow the occurrence of an interpenetrated 2D→3D framework. The cyclic voltammetric behavior and photocatalytic properties of POMOFs1 and2 were also investigated.