Luminactive Gold Complexes: Synthesis and Photophysics

这个无机、生物无机和有机金属化学项目的奖项支持凯斯西储大学托马斯·g·格雷教授的研究，该研究强调了金的有机金属化学和激发态性质(I)。主要目的是将金(I)中心安置到荧光有机分子上。金的重原子效应为荧光团的三重态光化学和光物理打开了方便之门。金可以被引入敏感的共轭分子中，这些分子可以吸收预定的波长。两种新的合成方法证明了金(I)片段通过碳金sigma键连接到芳香骨架上。第一种是碱基促进的金属转化，它将金与芳香分子的外围结合，具有广泛的通用性和功能上的耐受性。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)三唑氧基。光物理研究，包括静态和时间分辨发射测量，证明了金功能化芳烃的三态发光。这些活动背后的合成概念允许测量内部重原子效应（通过直接的碳金附着）和外部效应，其中金悬浮在光惰性间隔上的发射部分之上。各种日常应用要求材料是坚固的，可调谐的三态发射器。其中包括发光二极管技术、光敏化和生物标记。本研究还将通过发展偶氮二吡咯甲烷发色团第11组配合物的合成和表征的本科实验室练习，为化学教学做出贡献。这项研究也在培养本科生和研究生从事工业、政府、军队和学术界的科学事业。

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.