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Covalent Attachment of Thiophene Groups to Polyoxomolybdates or Polyoxotungstates for the Formation of Hybrid Films
Author(s) -
Saad Ali,
Anwar Nargis,
Rousseau Guillaume,
Mialane Pierre,
Marrot Jérôme,
Haouas Mohamed,
Taulelle Francis,
Mc Cormac Timothy,
Dolbecq Anne
Publication year - 2015
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.201500660
Subject(s) - chemistry , covalent bond , polymerization , phosphonate , thiophene , iminium , polymer chemistry , triphenylphosphine , solvent , ligand (biochemistry) , medicinal chemistry , nuclear chemistry , crystallography , inorganic chemistry , ion , organic chemistry , polymer , catalysis , receptor , biochemistry
A novel bisphosphonate ligand bearing a thiophene group (AleThio) was synthesized and its covalent grafting to polyoxometalates (POMs) investigated. The hybrid polyoxomolybdate [(Mo 3 O 8 ) 4 (O 3 PC(O)(C 3 H 6 NH 2 CH 2 C 4 H 3 S)PO 3 ) 4 ] 8– [Mo 12 (AleThio) 4 ] was synthesized in water by the reaction of Na 2 MoO 4 with AleThio. It is built of four {Mo VI 3 O 8 } units connected by phosphonate groups around a central Na + ion. The reaction of the trivacant [PW 9 O 34 ] 9– units with Co II or Ni II ions in the presence of AleThio led to the sandwich‐type anions [(PW 9 O 34 ) 2 (OH) 2 (H 2 O) 4 M 7 (O 3 PC(O)(C 3 H 6 NH 2 CH 2 C 4 H 3 S)PO 3 ) 2 ] 14– [M = Ni, Co; M 7 (AleThio) 2 ]. Salts soluble in organic solvent were prepared by cation‐exchange with bis(triphenylphosphine)iminium ions. 31 P NMR spectroscopy showed that Mo 12 (AleThio) 4 is stable in acidic medium (pH ≤ 4) while the M 7 (AleThio) 2 POMs are stable in alkaline medium (6 ≤ pH ≤ 13). Their cyclovoltammograms were recorded in solution. Attempts to surface immobilize the POMs through homo‐polymerization were unsuccessful but co‐polymerization employing 3‐methylthiophene led to polymeric films with covalently attached POMs.