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[{Ni4 (OH)3 AsO4 }4 (B-α-PW9 O34 )4 ](28-) : A New Polyoxometalate Structural Family with Catalytic Hydrogen
Hongjin Lv1, Yingnan Chi1, Jan van Leusen2
1Department of Chemistry and X-ray Crystallography Center, Emory University, 1515 Dickey Dr., Atlanta, Georgia 30322 (USA).
Abstract:
A new structural polyoxometalate motif, [{Ni4 (OH)3 AsO4 }4 (B-α-PW9 O34 )4 ](28-) , which contains the highest nuclearity structurally characterized multi-nickel-containing polyanion to date, has been synthesized and characterized by single-crystal X-ray diffraction, temperature-dependent magnetism and several other techniques. The unique central {Ni16 (OH)12 O4 (AsO4 )4 } core shows dominant ferromagnetic exchange interactions, with maximum χm T of 69.21 cm(3) K mol(-1) at 3.4 K. Significantly, this structurally unprecedented complex is an efficient, water-compatible, noble-metal-free catalyst for H2 production upon visible light irradiation (photosensitizer=[Ir(ppy)2 (dtbbpy)][PF6 ]; sacrificial electron donor=triethylamine or triethanolamine). The highest turnover number of approximately 580, corresponding to a best quantum yield of approximately 4.07 %, is achieved when using triethylamine as electron donor in the presence of water. The mechanism of this photodriven process has been probed by time-solved luminescence and by static emission quenching.
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