RUI: Synthesis and Photophysical Studies of Transition Metal Alkynyl Complexes for Applications in Photochemical Molecular Devices

在这个由化学系化学合成项目资助的项目中，弗曼大学化学系的Paul Wagenknecht教授将开发具有有趣光电特性的新型过渡金属炔基配合物。本研究的目标是利用这些过渡金属炔基配合物的特性来开发光电器件，即近红外发光传感器、有机发光二极管和将太阳能转换为存储的化学能或电能的系统（例如染料敏化太阳能电池）。此外，该项目将为器件化学领域的本科生、硕士和博士后提供优秀的培训。过渡金属炔基配合物显示出丰富的光物理性质，取代炔基配体既可以用于调节激发态，也可以作为电子和能量转移的管道。提出的合成包括旨在探索激发态光物理与分子结构之间关系的修饰。本项目将制备三类新的过渡金属炔基配合物，以回答以下问题：1)炔基二亚胺配体能否促进近红外镧系元素发射的Cr（III）敏化，以及Cr到Ln的能量转移速率如何受分子结构的影响？2)高场强三氟丙基配体的加入如何影响有机发光二极管感兴趣的发射配合物的激发态？3)是否可以控制炔基桥接Ti(IV)-Fe（II）组件中Fe（II）到Ti（IV）金属间电荷转移激发态的氧化还原性质，并利用其将太阳能转化为存储的化学能？

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Paul Wagenknecht of the Department of Chemistry at Furman University will develop new classes of transition metal alkynyl complexes with interesting optoelectronic properties. The goal of this research is to exploit the characteristics of these transition metal alkynyl complexes for the development of optoelectronic devices, namely near-infrared luminescent sensors, organic light emitting diodes, and systems for the conversion of solar energy into stored chemical energy or electricity (e.g. dye-sensitized solar cells). In addition, this project will provide excellent training of undergraduate, masters, and postdoctoral students in the area of device chemistry. Transition metal alkynyl complexes display a rich array of photophysical properties where substituted alkynyl ligands can be used both for the tuning of excited states and as conduits for electron- and energy-transfer. The proposed syntheses include modifications designed to probe the relationship between excited state photophysics and molecular architecture. In this project, three classes of new transition metal alkynyl complexes will be prepared to answer the following questions: 1) Can alkynyl-diimine ligands be used to facilitate Cr(III) sensitization of near-infrared lanthanide emission and how is the rate of the Cr to Ln energy transfer affected by the molecular architecture? 2) How does the inclusion of the high field strength trifluoropropynyl ligand impact the excited states of emissive complexes of interest for organic light emitting diodes? 3) Can the redox properties of the Fe(II) to Ti(IV) metal-to-metal charge-transfer excited state in alkynyl bridged Ti(IV)-Fe(II) assemblies be controlled and exploited for the conversion of solar energy into stored chemical energy?