Crystal structure and solid-state fluorescence of an oxomolybdenum(V)-benzylviologen electron donor-acceptor salt

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Solutions containing benzylviologen and the fluorescent oxo-d1 ion MoOBr4(CH3CN)- in acetonitrile slowly deposit crystals of the electron donor-acceptor complex (BV)[MoOBr4(H2O)]Br·CH3CN: C26H27Br5MoN3O2, triclinic, space group P1; a=11.349(1), b=16.1048(8), c=18.720(1) Å; α=71.961(5), β=76.375(7), γ=82.484(6)°; Z=4; R(F)=0.048, Rw(F)=0.046 for 4135 reflections and 668 parameters. The two independent Mo complex anions in the structure show MoO distances of 1.62(1) and 1.629(9) Å. The fluorescence spectrum of the solid complex is similar in shape and intensity to those of other salts of MovOBr4(H2O)- with non-quenching cations. The relatively intense fluorescence of solid (BV)[MoOBr4(H2O)]Br·CH3CN suggests that electron transfer from MovOBr4(H2O)-*(2E) to BV2+, although slightly favorable thermodynamically, does not compete effectively with its rapid fluorescence. © 1994.

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Inorganica Chimica Acta

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