Developing A Sustainable Metal Alkynyl Chemistry

开发可持续的金属炔基化学

• 批准号: 1764347
• 负责人: Tong Ren
• 金额: $ 53.46万
• 依托单位: Purdue 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 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1764347&HistoricalAwards=false
• 关键词: Developing; Sustainable; Metal; Alkynyl; Chemistry

The Chemical Synthesis Program of the Division of Chemistry supports the project by Professor Tong Ren. Professor Ren is a faculty member in the Department of Chemistry at Purdue University. He and his coworkers are developing new classes of metal alkynyl complexes with interesting photochemical properties. The goal of this research is to establish a unique family of donor-metal-alkynyl-acceptor complexes based on earth abundant metals, to study how electrons move within these molecules under sunlight, and to learn how to control such electron movement. This study may provide clues on how to improve molecular photovoltaic systems for the conversion of solar energy into electricity using earth abundant materials. The project involves both organic and inorganic syntheses and ultrafast spectroscopy, which provides broad training for both graduate and undergraduate students. Professor Ren's group is also actively engaging students underrepresented in science, and plays a significant role in bringing the state of arts equipment to the K-12 students in the rural areas of Indiana by enhancing their hands-on laboratory experience. This research and education program promotes US competitiveness through an exploration of sustainable systems for photovoltaics, photocatalysis, and molecular electronic devices.Transition metal acetylide compounds have been employed in a number of technologically important areas including photovoltaics, photo-catalysis and molecular electronic devices. The current project begins with the preparation of the symmetric and unsymmetric bis-alkynyl metal complexes supported by C-substituted cyclams. A special focus of the synthetic effort is the donor-bridge-acceptor (D-B-A) dyads, where D and A are respectively alkynyls capped with appropriate electron donor and acceptor, and B is the M(cyclam) unit. Besides the establishment of molecular geometry through single crystal X-ray diffraction, the degree of donor-acceptor interaction and its impact on redox and photophysical properties is assessed using voltammetric, spectroelectrochemical and steady-state emission spectroscopic techniques. Through the collaboration with both colleagues at Purdue and elsewhere, the investigators explore the attenuation of photoinduced electron transfer within the D-B-A dyad using both pump-probe and pump-pump-probe techniques. The transformative nature of the project lies in the promise of replacing precious metals in metal-alkynyl based materials with earth abundant 3d metals and discovering new electronic and optoelectronic properties. Professor Ren is striving to broaden the participation in chemical research enterprise by underrepresented groups on multiple levels from incoming freshman to junior faculty, and has maintained a diverse research group. Professor Ren and his coworkers also play an active role in Purdue's Science Express program, especially in introducing new teaching modules that reflect the heightened interest in sustainable chemistry.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.

化学划分的化学合成计划由Tong Ren教授支持该项目。 Ren教授是普渡大学化学系的教职员工。 他和他的同事正在开发具有有趣的光化学特性的新型金属烷基复合体。 这项研究的目的是建立一个基于地球丰富金属的独特供体 - 金属烷基 - 基于感受器络合物，以研究电子在阳光下如何在这些分子中移动，并学习如何控制这种电子运动。这项研究可能会提供有关如何改善分子光伏系统的线索，以将太阳能转化为使用地球丰富材料的电力。 该项目涉及有机和无机合成和超快光谱学，可为研究生和本科生提供广泛的培训。 Ren教授的小组还积极吸引学生在科学方面的分配不足，并且在将艺术设备的状况带入印第安纳州农村地区的K-12学生中发挥了重要作用，通过增强他们的动手实验室经验。该研究和教育计划通过探索用于光伏，光催化和分子电子设备的可持续系统来促进美国的竞争力。过渡金属乙酰基化合物已在许多技术上重要的领域采用，包括光伏，照片催化和分子电子设备。当前的项目始于制备由C取代的​​圆柱体支撑的对称和非对称的双卵母细胞金属配合物。合成工作的一个特殊重点是供体桥 - 受体（D-B-A）二元组，其中D和A分别用适当的电子供体和受体限制的藻类，而B是M（cyclam）单位。除了通过单晶体X射线衍射建立分子几何形状外，还使用伏安仪，光谱电极化学化学和稳态发射光谱技术评估了供体 - 受体相互作用的程度及其对氧化还原和光物理性能的影响。通过与普渡大学和其他地方的两个同事的合作，研究人员探索了使用Pump-probe和Pump-Pump-probe Techniques的D-B-A Dyad中光诱导的电子转移的衰减。该项目的变革性质在于有望用地球丰富的3D金属代替金属基因材料中的贵金属，并发现新的电子和光电特性。 Ren教授正在努力扩大来自代理新生到初级教职员工的多个级别的代表性不足的团体对化学研究企业的参与，并维持了一个多样化的研究小组。 Ren教授和他的同事在Purdue的科学快车计划中也发挥了积极的作用，尤其是在引入新的教学模块时，反映了对可持续化学的兴趣增强的新教学模块。该奖项反映了NSF的法定任务，并被认为是通过基金会的知识分子来评估的值得支持的优点和更广泛的影响审查标准。

项目成果

Chromium(III) Bis-alkynyl complexes supported by C-substituted cyclam MPC

• DOI: 10.1016/j.jorganchem.2021.122110
• 发表时间: 2021-12
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: Ashley J. Schuman;Madeline M. Mills;Leobardo Rodriguez Segura;Lyndsy A. Miller-Clark;T. Ren

Diruthenium aryl compounds – tuning of electrochemical responses and solubility

二钌芳基化合物 — 电化学响应和溶解度的调节

• DOI: 10.1039/d1dt03957a
• 发表时间: 2022
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Miller-Clark, Lyndsy A.;Christ, Peter E.;Ren, Tong
• 通讯作者: Ren, Tong

Forging Ru–C sp2 Bonds in Paddlewheel Complexes Using the Lithium–Halogen Exchange Reaction

利用锂-卤素交换反应在桨轮配合物中锻造 Ru-C sp2 键

• DOI: 10.1021/acs.inorgchem.8b03216
• 发表时间: 2019
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Raghavan, Adharsh;Mash, Brandon L.;Ren, Tong
• 通讯作者: Ren, Tong

Syntheses and material applications of Ru(II)(bisphosphine)2 alkynyls

• DOI: 10.1016/j.jorganchem.2021.122003
• 发表时间: 2021-10
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: Lyndsy A. Miller-Clark;T. Ren

New Synthetic Route for Cobalt(III) Dissymmetric Bisalkynyl Complexes Based on Cobalt(III)(cyclam)(C 2 NAP Mes ): New Synthetic Route for Cobalt(III) Dissymmetric Bisalkynyl Complexes Based on Cobalt(III)(cyclam)(C 2 NAP Mes )

基于钴(III)(cyclam)的钴(III)不对称双炔基配合物(C 2 NAP Mes )的合成新路线：基于钴(III)(cyclam)的钴(III)不对称双炔基配合物(C 2)的合成新路线

• DOI: 10.1002/ejic.201901070
• 发表时间: 2019
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: Banziger, Susannah D.;Zeller, Matthias;Ren, Tong
• 通讯作者: Ren, Tong