Lee Young-A, Eisenberg Richard
Department of Chemistry, University of Rochester, Rochester, NY 14627, USA.
J Am Chem Soc. 2003 Jul 2;125(26):7778-9. doi: 10.1021/ja034560k.
New dinuclear Au(I) complexes containing bridging thiouracilate and bis(diphenylphosphino)methane ligands have been synthesized and characterized structurally and spectroscopically. The compounds exhibit a unique behavior of solid-state luminescence tribochromism in which photoemission turns on upon gentle grinding of the sample and a sensitivity to pH in fluid solution. The emissive form in the solid state exhibits a bright blue or cyan emission upon irradiating at 375 nm. Structural studies show that the nonemissive form of the complexes has an extended helical ...Au...Au...Au... structure in the solid with weak aurophilic interactions, whereas the blue emissive form has a strong intermolecular aurophilic interaction in the solid that leads to an arrangement of dimers of dinuclear (Au2) complexes. Interconversion between the two forms can be carried out by either recrystallization for solid-state samples or by exposure to vapors of volatile acid or base for fluid solutions of the complexes.
已合成了含有桥联硫脲嘧啶和双（二苯基膦基）甲烷配体的新型双核金（I）配合物，并通过结构和光谱进行了表征。这些化合物表现出独特的固态发光三色性，即样品轻轻研磨时光发射开启，且在流体溶液中对pH敏感。固态下的发射形式在375nm照射时呈现亮蓝色或青色发射。结构研究表明，配合物的非发射形式在固体中具有扩展的螺旋……金……金……金……结构，金金相互作用较弱，而蓝色发射形式在固体中具有强的分子间金金相互作用，导致双核（Au2）配合物二聚体的排列。两种形式之间的相互转化可以通过固态样品的重结晶或配合物流体溶液暴露于挥发性酸或碱的蒸汽中来实现。
