Departament de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.
Inorg Chem. 2012 Jul 16;51(14):7636-41. doi: 10.1021/ic300609f. Epub 2012 Jun 28.
The systematic analysis of the luminescence of a series of alkynyl gold derivatives with general formulas [(diphos)(AuC≡Cpy)(2)] (diphosphane =2,2'-bis(diphenylphosphanyl)propane or dppip (1), bis(diphenylphosphanyl)acetylene or dppa (2), 1,2-bis(diphenylphosphanyl)ethane or dppe (3) and 1,4-bis(diphenylphosphanyl)butane or dppb, (4), has shown a straightforward correlation between the Au(I)···Au(I) distance and the emission quantum yields and decaytimes. The analysis of the decaytimes, quantum yields and thus, the corresponding calculated rate constants demonstrated the existence of a correlation between Au(I)···Au(I) distance and the radiative rate constant for the deactivation of the emissive triplet states. It was concluded that the increased emission of these compounds results from the increase in spin-orbit coupling that favors the spin forbidden transition to the singlet ground state.
系统分析了一系列具有通式[(diphos)(AuC≡Cpy)(2)]的炔基金衍生物，其中 diphosphane =2,2'-双（二苯基膦基）丙烷或 dppip（1）、二（二苯基膦基）乙炔或 dppa（2）、1,2-双（二苯基膦基）乙烷或 dppe（3）和 1,4-双（二苯基膦基）丁烷或 dppb（4）。结果表明，金（I）···金（I）距离与发射量子产率和衰减时间之间存在直接关系。对衰减时间、量子产率以及相应的计算速率常数的分析表明，金（I）···金（I）距离与三重态激发态的辐射速率常数之间存在相关性。结论是，这些化合物的发射增加是由于自旋轨道耦合的增加，有利于自旋禁阻跃迁到单重基态。
