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.

化学系化学合成计划支持同仁教授的项目。任教授是普渡大学化学系的教员。他和他的同事们正在开发具有有趣的光化学性质的新型金属炔基络合物。本研究的目标是建立一个独特的基于地球上丰富的金属的给体-金属-炔基-受体络合物家族，研究这些分子中的电子在阳光下是如何运动的，并学习如何控制这种电子运动。这项研究可能会为如何利用地球上丰富的材料改进分子光伏系统将太阳能转化为电能提供线索。该项目涉及有机和无机合成以及超快光谱学，为研究生和本科生提供广泛的培训。任教授的团队也在积极吸引在理科方面人数较少的学生，并通过增强印第安纳州农村地区K-12学生的动手实验室体验，在将最先进的设备带给印第安纳州农村地区的学生方面发挥了重要作用。这个研究和教育项目通过探索光伏、光催化和分子电子器件的可持续系统来提升美国的竞争力。过渡金属乙酰化合物已被用于许多重要的技术领域，包括光伏、光催化和分子电子器件。本项目首先制备了由C-取代环支撑的对称和不对称的双炔金属络合物。其中D和A分别是以合适的电子给体和受体为封端的炔基，B是M(环)单元。除了通过单晶X射线衍射法建立分子几何结构外，还利用伏安法、光谱电化学法和稳态发射光谱技术评估了给体-受体相互作用的程度及其对氧化还原和光物理性质的影响。通过与普渡大学和其他地方的同事合作，研究人员使用泵浦-探测和泵浦-探测技术探索D-B-A二元体中光致电子转移的衰减。该项目的变革性在于有望用地球上丰富的3D金属取代金属-炔基材料中的贵金属，并发现新的电子和光电特性。任教授正在努力扩大对化学研究事业的参与，从新生到初级教员，在多个层面上代表不足的群体，并保持了一个多元化的研究群体。任教授和他的同事还在普渡大学的科学快车计划中发挥了积极作用，特别是在引入新的教学模块方面，这些模块反映了人们对可持续化学的高度兴趣。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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

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

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

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

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