Hydrolysis to the first dumbbell-like high-nuclearity bismuth-oxo cluster [Bi12(μ3-OH)4(μ2-OH)2(μ3-O)8(μ4-O)2(NO3)6]4+: Synthesis, structure and spectroscopic characterizations

The first dumbbell-like high-nuclearity bismuth-oxo cluster [Bi-12(mu(3)-OH)(4)(mu(2)-OH)(2)(mu(3)-O)(8)(mu(4)-O)(2)(NO3)(6)](NO3)(4)center dot 6H(2)O was obtained by diffusing ethanol into the hydrolysate of Bi(NO3)(3) aqueous solution. The dumbbell consists of two Bi-O bonds as the handle and two [Bi-6(mu(3)-OH)(2)(mu(2)-OH)(mu(3)-O)(4)(mu(4)-O)] subunits as the bells. The bell can be regarded as a piercing bracelet-like ring consisted of six edge-sharing tetragons with one cross section enveloped by one mu(3)-O linking three Bi(111) atoms and the other connected by one mu(2)-O as a open cover. The structure is further stabilized by the interactions of Bi...Bi, Bi...O and hydrogen bondings. The optical gap of 2.85 eV suggests that the title compound behaves as semiconductors. The title compound features a blue fluorescence at 441 nm, which is assigned to P-1(1)-S-1(0) and P-3-S-1(0), transitions from the s(2) electron of Bi3+ cation. (c) 2007 Elsevier B.V. All rights reserved.