Design of New Ru(II) Complexes to Control Excited State Reactivity

控制激发态反应性的新型 Ru(II) 配合物的设计

• 批准号: 1800395
• 负责人: Claudia Turro
• 金额: $ 75万
• 依托单位: Ohio State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-01 至 2021-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800395&HistoricalAwards=false
• 关键词: Design; New; Ru; II; Complexes

In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Claudia Turro of the Department of Chemistry and Biochemistry at The Ohio State University works in collaboration with Professor Kim Dunbar (Texas A&M University) and Professor Jeremy Kodanko (Wayne State University) investigate fundamental processes in inorganic photochemistry. This project seeks to understand the fundamental steps that take place on ultrafast (femtosecond to picosecond) time scales after a transition metal complex absorbs a photon of light. New ruthenium complexes are designed, synthesized and studied to determine how their excited state processes and photochemistry depend on variation in structure. Transition metal complexes studied in this research are important in applications that range from solar energy conversion to the delivery of drugs for phototherapy. This collaborative team is also well positioned to provide the highest level of education and training for students underrepresented in science.The central goal of this project is to understand the basic principles that govern the photophysical processes in ruthenium II complexes at early times, including the factors that control efficient photosubstitution and dual-activity compounds. New ruthenium complexes are designed, synthesized and studied to test theories about how variation in structure affects photochemistry and photophysics. The mechanism by which two different photoactive states are populated in these ruthenium complexes remains unknown and is counter to the rules of photochemistry developed for organic molecules. Photoinduced ligand release using ruthenium II complexes is highly dependent on the identity of both the leaving and ancillary ligands. One hypothesis being tested to explain this structural dependence is that fast population of the metal-centered ligand field state is required for ligand exchange to take place. It is yet unknown if this occurs through direct intersystem crossing from the singlet manifold or from a vibrationally hot triplet state. The basic knowledge gained regarding photoinduced ligand exchange also aids in the design of complexes that eliminate the exchange process in order to increase the lifetime of the metal-to-ligand charge transfer state. This is an important factor in solar energy conversion. The project also focuses on the design and synthesis of new complexes that release a wider range of ligands through irradiation with visible or low energy near-infrared light. Transition metal complexes studied in this research have potential applications that include solar energy conversion and phototherapy. This collaborative research provides students with training in diverse research skills.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、动力学机制B计划资助的项目中，俄亥俄州州立大学化学和生物化学系的Claudia Turro教授与Kim Dunbar教授（德克萨斯A M大学）和Jeremy Kodanko教授（韦恩州立大学）合作研究无机光化学的基本过程。该项目旨在了解过渡金属络合物吸收光子后超快（飞秒至皮秒）时间尺度上发生的基本步骤。新的钌配合物的设计，合成和研究，以确定它们的激发态过程和光化学如何依赖于结构的变化。本研究中研究的过渡金属络合物在从太阳能转换到光疗药物输送的应用中非常重要。这个合作团队也有很好的定位，为学生提供最高水平的教育和培训在科学中的代表性。这个项目的中心目标是了解的基本原则，支配钌II络合物的电子物理过程在早期，包括控制有效的光取代和双活性化合物的因素。新的钌配合物的设计，合成和研究，以测试有关结构的变化如何影响光化学和光物理学的理论。 在这些钌络合物中填充两种不同的光活性状态的机制仍然未知，并且与为有机分子开发的光化学规则相反。使用钌II络合物的光诱导配体释放高度依赖于离去配体和辅助配体两者的身份。 一个假设正在测试，以解释这种结构的依赖性是，快速人口的金属为中心的配体场状态是需要配体交换发生。 目前还不清楚这是通过从单重态歧管或从振动热三重态的直接系统间穿越发生的。关于光诱导配体交换获得的基本知识也有助于设计消除交换过程的络合物，以增加金属-配体电荷转移状态的寿命。 这是太阳能转换的一个重要因素。该项目还侧重于设计和合成新的复合物，通过可见光或低能近红外光照射释放更广泛的配体。本研究中所研究的过渡金属配合物具有潜在的应用，包括太阳能转换和光疗。这项合作研究为学生提供了多样化的研究技能培训。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估来支持。

项目成果

Electron injection into titanium dioxide by panchromatic dirhodium photosensitizers with low energy red light

低能红光全色二铑光敏剂将电子注入二氧化钛

• DOI: 10.1039/c9cc04677a
• 发表时间: 2019
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Xue, Congcong;Sayre, Hannah J.;Turro, Claudia
• 通讯作者: Turro, Claudia

Dynamic orientation control of bimolecular electron transfer at charged micelle surfaces

带电胶束表面双分子电子转移的动态取向控制

• DOI: 10.1063/5.0018584
• 发表时间: 2020
• 期刊: The Journal of Chemical Physics
• 作者: Piechota, Eric J.;Turro, Claudia
• 通讯作者: Turro, Claudia

Unusually Slow Internal Conversion in N-Heterocyclic Carbene/Carbanion Cyclometallated Ru(II) Complexes: A Hammett Relationship

N-杂环卡宾/碳负离子环金属化 Ru(II) 配合物中异常缓慢的内转化：哈米特关系

• DOI: 10.1021/acs.jpca.9b00858
• 发表时间: 2019
• 期刊: The Journal of Physical Chemistry A
• 作者: Kender, William T.;Turro, Claudia
• 通讯作者: Turro, Claudia

Unexpected Role of Ru(II) Orbital and Spin Contribution on Photoinduced Ligand Exchange: New Mechanism To Access the Photodynamic Therapy Window

• DOI: 10.1021/acs.jpcc.9b01576
• 发表时间: 2019-04-25
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY C
• 影响因子: 3.7
• 作者: Loftus, Lauren M.;Al-Afyouni, Kathlyn F.;Turro, Claudia
• 通讯作者: Turro, Claudia