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Three Polymeric Polyoxometalate Compounds Based on Twisted Poly‐Keggin Chains
Author(s) -
Ren Yuanhang,
Hu Yichen,
Kong Zuping,
Gu Min,
Yue Bin,
He Heyong
Publication year - 2013
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.201201374
Subject(s) - polyoxometalate , chemistry , keggin structure , x ray photoelectron spectroscopy , crystallography , cyclic voltammetry , polymerization , valence (chemistry) , electrochemistry , catalysis , polymer , organic chemistry , electrode , physics , nuclear magnetic resonance
Three polymeric polyoxometalate (POM) compounds, [PMo VI 10 Mo V 2 O 39 ](C 2 N 4 H 4 ) 2 [(CH 3 ) 4 N] 3 · H 2 O ( 1 ), [PW 11 CuO 39 ] 2 · [Cu(en) 2 H 2 O] 4 · [(CH 3 ) 4 N] 2 · 6H 2 O (en = ethenediamine) ( 2 ), and [SiW 11 CuO 39 ] 2 · [Cu(en) 2 ] 4 · [Cu(en) 2 H 2 O] 2 · 10H 2 O ( 3 ) were isolated under hydrothermal conditions. Compound 1 contains one‐dimensional twisted poly‐Keggin chains that consist of two‐electron‐reduced Keggin units through Mo V –O t –Mo V bridges. Compounds 2 and 3 contain one‐dimensional twisted poly‐Keggin chains that consist of Cu‐monosubstituted Keggin units through W–O t –Cu bridges. Twisted chains are formed due to the different orientations of the Keggin units during polymerization. The compounds were characterized by single‐crystal X‐ray diffraction, elemental analysis, IR, X‐ray photoelectron spectroscopy (XPS), thermogravimetry (TG), and cyclic voltammetry. The driving force for polymerization by the sharing of a terminal oxygen atom per POM unit likely arises from the existence of a low‐valence metal (Mo V or Cu II ), which reduces the charge density of each POM unit.