“金属配合物激发态的基础与应用研究”年度报告  

Annual Report of "Excited States of Metal Complexes:Basic Research and Applications"

作　　者：支志明[1] 程刚[2] 陈勇[3] Zhi Zhiming;Cheng Gang;Chen Yong(Shenzhen Research Institute,University of Hong Kong;Jilin University;Technical Institute of Physics and Chemistry,Chinese Academy of Sciences)

机构地区：[1]香港大学深圳研究院 [2]吉林大学 [3]中国科学院理化技术研究所

出　　处：《科技资讯》2016年第23期175-176,共2页Science & Technology Information

摘　　要：(1)应用量子理论,在Marcus理论基础之上,研究了蓝色磷光体系三芳基Pt配合物的发光性质,并提出了量子效率优化方案。扭曲结构D-A分子具有局域和电荷转移杂化态HLCT性质,在理论上形成单三线态激子时也有可能突破量子自旋统计,即单线态激子的形成比例会超过25%,同时材料本身也有较高的光致发光效率,因而在电致发光器件方面可能会有很好的性能。(2)设计合成了一系列含有配位碳原子的四齿配体,并进一步合成了基于这些刚性配体的铂(II)配合物,通过稳态光谱和超快光谱对铂(II)配合物的光物理性质进行了深入研究,利用密度泛函理论对配合物的基态和激发态性质进行了理论分析,总结了电荷跃迁位置和类型变化的控制因素,探索了这些强磷光材料在光电器件中的应用。(3)在强磷光发射和长激发态寿命的金(III)和钯(II)配合物及其在光催化太阳能转换、能量上转换、双光子吸收和磷光OLED中的应用等方面取得了阶段性进展。(4)在廉价金属(锌、铜和钨)配合物荧光/磷光材料的设计合成及光电应用、不含金属的有机小分子磷光发射方面取得突破性进展,观察到了有机分子的电致磷光。(5)以三核吡唑基d10金属(Cu I,Ag I,Au I)配位单元为主要研究对象,通过合成和配体设计对三核单元间的聚集态结构进行调节,实现了对其聚集体的光物理过程的调控。(6)利用晶态光功能配位超分子聚集体的协同作用、异相反应和动态孔性,进行了研磨致发光变色、异相催化和染料降解、选择性发光传感等应用研究。对于非晶相光功能配位超分子聚集体这类软物质材料,主要探索了其在纳米结构和生物体系中的抗癌活性等方面的应用研究。(7)将动态共价键引入到超分子聚集体的合成中,通过次级组分自组装的技术,成功制备了两类新型的咪唑配位超分子聚集体,首次实现了次级组分�(1)Combining Marcus theory with tight binding DFT, a new high efficient luminescent material was designed basedon the detailed exploration of excited state and radiation constant of a serials of Pt complex. A twisting donor–acceptor TPANZPexhibits fluorescent emission through a hybridized local and HLCT. (2)Designed and synthesized a series of rigid Pt(II)complexes with tetradentate ligands. Through a combination of ultra-fast spectroscopic characterizations and theoreticalcalculations, we investigated detailedly the photophysical properties of these metal complexes, summarized the basic rules fortuning of the excited-state properties of metal complexes, and explored their applications in optoelectronic materials. (3)Madeprogress in the application of strongly luminescent Au(III) and Pd(II) complexes with long-lived excited states on photophysics,photochemistry, and OLEDs. (4)designed and synthesized inexpensive metal complexes (Zn, Cu, W complexes) and organicmolecules for photocatalysis and OLEDs. (5)Taking trinuclear d10 metal pyrazolates as structural units, the regulation ofphotophysical process of these aggregates were realized by adjusting the structure of these trinuclear aggregates. (6) Utilizingthe inherent properties of synergistic interactions, heterogeneous reactions, dynamic porosity in crystalline aggregates, theapplication of mechanochromism, heterogeneous catalysis, dye degradation and selective luminescence sensor were achieved. (7)Introducing dynamic covalent bond into the synthesis of coordination supramolecular aggregates, two kinds of imidazolatecoordination supramolecular aggregates were prepared through subcomponent self-assembly. (8) Designed and prepared 16 metalcomplexes as photosensitizers and catalysts, systematically investigated their UV absorption, electron excitation and transferprocesses. Investigated the photocatalytic hydrogen production activities of theses complexes in the presence of a sacrificialelectron donor in a three component photocatalytic system. (9) Designed and s

关 键 词：金属配合物 理论计算 高效率 长激发态寿命 有机发光器件 配位超分子聚集体 磷光 光催化 

分 类 号：O641.4[理学—物理化学]