Luminactive Gold Complexes: Synthesis and Photophysics

化学合成(SYN)项目的这一奖项支持凯斯西储大学的Thomas Gray教授开展有机金属金化学基础研究的工作。(配体)金(I)片段取代末端氢与碳结合。黄金在受控位置被嫁接到有机支架上。敏感官能团得以保留，避免了刺激性试剂。金原子在光激发下促进了三重激发态的布居。这些三重态持续微秒或更长时间。金(I)有机金属化合物的超快动力学研究揭示了(膦)金(I)芳香族化合物的吸收和衰减特性。一些边缘带有金色的共轭发色团正在制备中。正在测量这些化合物的结构和光学性质。吸收光谱和发射光谱，以及态与态之间的动力学，可以用含时密度泛函理论计算来理解。格雷集团还在开发形成稳定的碳金键的合成方法。这些反应形成可分离、易于表征和易于操作的有机金属化合物。这项研究对催化、发光二极管结构和薄膜沉积等方面的应用具有重要意义。这项工作还将为金属有机合成和光物理表征的本科生实验室做出贡献。这一活动应用了金点击化学，即铜催化的金(I)炔基与有机叠氮化合物的环加成反应。用静态发射光谱和时间分辨发射光谱对所合成的三氮唑配合物进行了表征。支持的研究正在为工业、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 Chemical Synthesis (SYN) program supports work by Professor Thomas Gray at Case Western Reserve University to carry out fundamental studies in organometallic gold chemistry. (Ligand)gold(I) fragments bind to carbon in place of terminal hydrogens. Gold is grafted to organic scaffolds at controlled positions. Sensitive functional groups survive, and harsh reagents are avoided. The gold atom promotes population of triplet excited states upon light-excitation. These triplet states persist for microseconds or longer. Ultrafast kinetics studies of gold(I) organometallics are revealing the absorption and decay characteristics of (phosphine)gold(I) aromatics. A number of conjugated chromophores, with gold at the edges, are being prepared. The structural and optical properties of these compounds are being measured. Absorption and emission spectra, and state-to-state dynamics, are understood with time-dependent density-functional theory calculations. The Gray group is also developing synthetic methods that form stable carbon-gold bonds. These reactions form isolable, readily characterized, and easily handled organometallics. This research has relevance to such applications as catalysis, light-emitting diode construction, and film deposition, among others. The work will also contribute to an undergraduate laboratory in organometallic synthesis and in photophysical characterization. This activity applies gold click-chemistry, a copper-mediated cycloaddition of gold(I) alkynyls with organic azides. The resulting triazolate complexes are characterized by static and time-resolved emission spectroscopy. The supported research is training undergraduate and graduate students for scientific careers in industry, government, the military, and academia.