CAS: Ultrafast Spectroscopy and Photoisomerization of Iron Sulfoxide Complexes

CAS：亚硫酸铁配合物的超快光谱和光异构化

• 批准号: 2247761
• 负责人: Jeffrey Rack
• 金额: $ 46.84万
• 依托单位: University of New Mexico
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-06-01 至 2026-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247761&HistoricalAwards=false
• 关键词: CAS; Ultrafast; Spectroscopy; Photoisomerization; Iron

With support from the Chemical Structure, Dynamics & Mechanisms-B (CSDM-B) Program of the Chemistry Division (CHE), and the Established Program to Stimulate Competitive Research (EPSCoR), Professor Jeffrey Rack of the University of New Mexico is developing new classes of iron complexes with interesting spectroscopic and magneto-optical properties. The goal of this research is to design new photoactive iron complexes with sulfoxide ligands. The project lies at the interface of organic, inorganic, and physical chemistry, and is appropriate for education of scientists at all levels of experience. The University of New Mexico is a majority minority institution and the Rack research group is works to provide the highest level of education and training for students underrepresented in science and will continue to do so under this award. Outreach activities involving the training of high school and middle chemistry teachers is part of the research project. The proposed work details a research plan to create photoactive iron polypyridine sulfoxide complexes. The goal of this work is to discover if phototriggered sulfoxide isomerization can be supported on iron centers in a fashion similar to that on related ruthenium complexes. In ruthenium complexes, 3MLCT excitation prompts transient Ru3+ formation, which induces excited state isomerization of the sulfoxide from S-bonded to O-bonded. Professor Rack and his research team aim to reproduce this photochemistry on iron with the objective of stabilizing high or intermediate spin states with the O-bonded coordination mode. There are two major challenges that must be met to observe this chemistry on iron: 3MCLT (metal-to-ligand charge-transfer) states on iron are rare due to the primogenic effect and sulfoxide isomerization on iron has not been reported. Preliminary results provide evidence that these challenges can be overcome and that the goal of achieving S- to O-sulfoxide bonding on iron can be achieved. If successful, the ability to achieve such intermediate to high spin state Fe-sulfoxide complexes would be a significant advance for the field as this would bring this chemistry into the realm of earth abundant transition metal space, and open up an important new avenue of exploration for organometallic chemists.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.

在化学结构，动力学和机制-B（CSDM-B）计划（CHE）和刺激竞争性研究的既定计划的支持下，新墨西哥大学的Jeffrey Rack教授正在开发具有有趣的Spectroscopic和Magneto-Proptorty Properties的新型铁配合物。这项研究的目的是设计新的光活性铁配合物，该配体具有硫氧化物配体。该项目在于有机，无机和物理化学的界面，适合各种经验的科学家教育。新墨西哥大学是少数族裔机构，Rack Research Group努力为科学领域不足的学生提供最高水平的教育和培训，并将在此奖项下继续这样做。研究项目的一部分是涉及高中和中学教师培训的外展活动。提出的工作详细介绍了一项研究计划，以创建光活性铁polypyridine磺胺氧化物络合物。这项工作的目的是发现是否可以在铁中心上以类似于相关的钌络合物的方式在铁中心上支持光触发的硫化氧化异构化。在芳族复合物中，3MLCT激发促使瞬时RU3+形成，从而诱导硫氧化磺酰化的激发态异构化，从S键到O键。 RACK教授及其研究团队旨在在铁上复制这种光化学，目的是通过O键合协调模式稳定高或中间的自旋状态。在铁上观察这种化学的化学：3MCLT（金属到配体的电荷转移）在铁上必须面临两个主要挑战，这是很少见的，这是由于原始作用和硫氧化物异构化对铁的报道。初步结果提供了可以克服这些挑战的证据，并且可以实现S-到O-硫氧化型在铁上的目标。 如果成功，那么实现此类中间至高旋转状态二硫代氧化物络合物的能力将是该领域的重大进步，因为这将使这种化学变成地球丰富的过渡金属领域，并为有机金属化学家开辟了重要的新探索途径。该奖项是NSF的法定任务，反映出值得通过评估的构成师的构成者的宗教师的依据，并反映了构成的依据。