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Organic–Inorganic Hybrid Clusters Assembled from Phosphomolybdate Anions and Thioarylated Tetrathiafulvalenes with Diversiform Electron States and Configurations
Author(s) -
Zhang Shangxi,
Cao Meng,
Jiang Xinde,
Xu Sheng,
Dai Xin,
Liu Yang,
Wang Zhenxi
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201901185
Subject(s) - polyoxometalate , chemistry , tetrathiafulvalene , intermolecular force , hybrid material , electrochemistry , crystallography , valence (chemistry) , electron transfer , aryl , inorganic chemistry , molecule , photochemistry , organic chemistry , catalysis , electrode , alkyl
A series of organic–inorganic hybrid clusters comprising thioarylated tetrathiafulvalene derivatives (A‐S‐TTFs) and Keggin‐type polyoxometalates have been prepared via proton‐induced intermolecular charge transfer or electrochemical oxidation methods, and their structural features have been intensively studied by X‐ray diffraction. The generation of co‐crystals occurs due to the flexible structure of the A‐S‐TTF and its electrostatic interaction with the polyoxometalate anions. The complexes can be divided into three types, i.e., type I, type II, and type III, which have organic/inorganic ratios of 3:1, 2:1, and 1:1, respectively. Multiple intermolecular interactions are observed between the organic and inorganic moieties, which stabilize the structures of the resulting hybrid clusters. In the clusters, Ar‐S‐TTFs are oxidized into radical cations [except in complex (TTF4) · (PMA) · (TBA), where TTF4 is presented as a +2 cation]. There are two factors affecting the packing styles and compositions of the hybrid clusters: 1) valence state of the Ar‐S‐TTF and 2) volume of the aryl groups thereon.