Luminactive Gold Complexes: Synthesis and Photophysics

无机化学、生物无机化学和金属有机化学项目的这一奖项支持凯斯西储大学的托马斯·G·格雷教授的研究，他强调了金的有机金属化学和激发态性质(I)。主要的目标是将金(I)中心定位到荧光有机分子上。金的重原子效应开启了荧光团的三态光化学和光物理的途径。金可以被引入敏感的共轭分子中，这些分子吸收预定的波长。证明了两种新的合成方法，其中金(I)片段通过碳-金西格玛键连接到芳香骨架上。第一种是碱促进的金属转移反应，它将金结合到芳香族分子的外围，具有广泛的普遍性和功能耐受性。第二种是金(I)叠氮化物与末端炔的[3+2]环加成反应，生成金(I)三唑基团。光物理研究，包括静态和时间分辨发射测量，证明了金官能化的芳香族化合物的三态发光。作为这些活动基础的合成概念允许测量内部重原子效应(通过直接的碳金结合)和外部效应，其中金被悬浮在光惰性间隔物上的发射部分上方。各种日常应用需要坚固的、可调的三重态发射体材料。其中包括发光二极管技术、光敏化和生物标记。这项研究还将通过制定一项关于合成和表征氮杂二吡咯亚甲基发色团第11族络合物的本科生实验室练习，为化学教育学作出贡献。这项研究还在为工业、政府、军事和学术界的科学职业培养本科生和研究生。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Thomas G. Gray at Case Western Reserve University that emphasizes the organometallic chemistry and excited-state properties of gold(I). The leading objective is emplacement of gold(I) centers onto fluorescent organic molecules. The heavy-atom effect of gold opens access to the fluorophores' triplet-state photochemistry and photophysics. Gold can be introduced in sensitive, conjugated molecules that absorb at preordained wavelengths. Two new synthetic methods are demonstrated where gold(I) fragments are attached to aromatic skeletons through carbon-gold sigma bonds. The first of these, base-promoted transmetallation, binds gold to the peripheries of aromatic molecules and is broadly general and functionally tolerant. The second is a [3 + 2] cycloaddition reaction of gold(I) azides with terminal alkynes that yields gold(I) triazolato moieties. Photophysical studies, which include static and time- resolved emission measurements, demonstrate triplet-state luminescence from aromatics functionalized with gold. The synthesis concepts that underlie these activities permit measurement of both internal heavy-atom effects (through direct carbon-gold attachment) and of external effects, where gold is suspended above an emitting moiety upon a photoinert spacer. A variety of day-to-day applications call for materials that are robust, tunable triplet-state emitters. Among these are light-emitting diode technology, photosensitization, and biological labeling. This research will also contribute to chemical pedagogy through the development of an undergraduate laboratory exercise in the synthesis and characterization of group 11 complexes of azadipyrromethene chromophores. This research is also training undergraduate and graduate students for scientific careers in industry, government, the military, and academia.