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Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Construction of (3,6)-connected polyoxometalate-based metal-organic frameworks (POMOFs) from triangular carboxylate
Bao-Xia Dong1, Hua-Bo Chen, Yi-Chen Wu
1School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, P. R. China. bxdong@yzu.edu.cn ylteng@yzu.edu.cn.
Abstract:
Using the methodology of extension of reduced transition metal-grafted ε-Keggin polyoxoanions with two types of terphenyl-based tricarboxylates of H3L1 (3,5',3''-position substitution) and H3L2 (4,5',4''-position substitution) we isolated two (3,6)-connected 3D polyoxometalate-based metal-organic frameworks, [TBA]3[H3PMo12O40][Zn4L2] (1, YZU-105), and [TPA]3[H3PMo12O40][Zn4L1]·0.5H2O (2, YZU-106) (H3L1 = [1,1';3',1''-terphenyl]-3,5',3''-tricarboxylic acid; H3L2 = [1,1';3',1''-terphenyl]-4,5',4''-tricarboxylic acid; TBA = tetrabutylammonium; TPA = tetrapropylammonium). In both compounds, the building block was the dimerized form of Zn4-{ε-H3PMo12O40}. Such dimerization left six anchoring points for each dimer and, as a result, a 6-connected node was formed. Compounds 1 and 2 exhibited topologies of (4·85)3(4·82)6 and (65·10)3(63)6, respectively. This work illustrates that use of tri-carboxylate substitutions in different positions (3,5',3''-position/4,5',4''-position) in tripodal terphenyl-based ligands allows different extents of twisting of the peripheral aromatic ring with respect to the central ring, thereby giving rise to different extending directions and symmetries.
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