RUI: CAS: Alkynyl Complexes of Titanium(IV) and Platinum(II): Phosphors, Photocatalysts, and Fundamental Photophysics

RUI：CAS：钛 (IV) 和铂 (II) 的炔基配合物：磷光体、光催化剂和基础光物理学

• 批准号: 2055326
• 负责人: Paul Wagenknecht
• 金额: $ 33.74万
• 依托单位: Furman University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2055326&HistoricalAwards=false
• 关键词: RUI; CAS; Alkynyl; Complexes; Titanium

In this RUI project, funded by the Chemical Structure, Dynamics & Mechanism B Program of the Chemistry Division, Professor Paul Wagenknecht of the Department of Chemistry at Furman University is developing new transition-metal alkynyl complexes for use as photocatalysts and as phosphors. Transition-metal photocatalysts are crucial components in organic synthesis and in systems for the conversion of solar energy into electricity and/or chemical fuels. Professor Wagenknecht aims to use complexes of earth-abundant elements to replace precious metal photocatalysts. Transition-metal phosphors are essential components of organic light-emitting diodes (OLEDs). The development of phosphors for OLEDs in Professor Wagenknecht’s group involves a set of complexes designed to enhance blue emission, which remains a technical challenge. These complexes also show promise for the development of single-component white OLEDs (WOLEDs). Students involved in the proposed activities will be trained in methods directly related to device chemistry and the conversion of solar energy to stored chemical energy. This will result in the development of a STEM workforce prepared to solve problems of serious social significance. Students in the Professor Wagenknecht’s laboratory are also active in after-hours tutoring programs and/or providing chemistry demonstrations to local elementary and middle schools. They are also active in outreach to high school students and high school teachers. Recent reports demonstrate that complexes of earth-abundant metals with ligand-to-metal charge transfer excited states represent a new class of possible photocatalysts. Titanocenes previously developed in Professor Wagenknecht’s laboratory have proven to be a synthetically accessible class of compounds with excited-state redox potentials appropriate for use as photocatalysts and as dyes for dye-sensitized solar cells (DSSCs). New alkynyl-titanocenes with rigid structures and/or with Cu(I) coordinated between the alkynes are proposed to have higher stability and longer excited-state lifetimes and will be compared to those without such modification. This could lead to a stronger understanding of the photophysical principles necessary to design first-row transition-metal sensitizers. Professor Wagenknecht’s group has developed a titanocene precursor with carboxylate anchoring groups so that a range of titanocenes can be prepared and appended to titanium dioxide to investigate their possible use as sensitizers in DSSCs and investigate principles of charge injection. The Pt-alkynyl complexes proposed are being prepared to mechanistically investigate the role of the trifluoropropynyl ligand in blue-shifting emission while maintaining high phosphorescence quantum yields. Furthermore, the interplay between the blue monomer emission and the orange excimer emission will be investigated for possible applications in WOLED devices. These activities are supported by a robust computational component.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在这个由化学部化学结构、动力学和机理B项目资助的RUI项目中，弗曼大学化学系的Paul Wagenknecht教授正在开发新的过渡金属炔基配合物，用于光催化剂和荧光粉。过渡金属光催化剂是有机合成和将太阳能转化为电能和/或化学燃料的系统中的关键组成部分。Wagenknecht教授的目标是使用富含地球元素的络合物来取代贵金属光催化剂。过渡金属荧光粉是有机发光二极管（oled）的重要组成部分。在Wagenknecht教授的小组中，用于oled的荧光粉的开发涉及一系列旨在增强蓝色发射的复合物，这仍然是一个技术挑战。这些配合物也显示出发展单组分白色oled （WOLEDs）的希望。参与拟议活动的学生将接受与装置化学和将太阳能转化为储存的化学能直接相关的方法的培训。这将导致STEM劳动力的发展，为解决具有严重社会意义的问题做好准备。Wagenknecht教授实验室的学生也积极参加课外辅导项目和/或为当地中小学提供化学演示。他们还积极向高中学生和高中教师伸出援手。最近的报道表明，具有配体到金属电荷转移激发态的地球上丰富的金属配合物代表了一类新的可能的光催化剂。Wagenknecht教授的实验室先前开发的钛茂烯已被证明是一种可合成的化合物，具有激发态氧化还原电位，适合用作光催化剂和染料敏化太阳能电池（DSSCs）的染料。具有刚性结构和/或在炔间配位Cu(I)的新型炔基钛茂烯具有更高的稳定性和更长的激发态寿命，并将与未进行此类修饰的炔基钛茂烯进行比较。这可能会导致对设计第一排过渡金属敏化剂所需的光物理原理的更强理解。Wagenknecht教授的团队已经开发出一种具有羧酸锚定基团的二茂钛前驱体，这样就可以制备一系列的二茂钛并将其附加到二氧化钛上，以研究它们在DSSCs中作为增敏剂的可能用途，并研究电荷注入原理。所提出的pt -炔基配合物的制备是为了在保持高磷光量子产率的同时，从机理上研究三氟丙基配体在蓝移发射中的作用。此外，蓝色单体发射和橙色准分子发射之间的相互作用将被研究在WOLED器件中的可能应用。这些活动由一个健壮的计算组件支持。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。