Mechanistic Studies of Dipole Effects on Electronic Coupling in Charge Transfer Implemented as Photoinduced Dynamics of Intramolecular Hole Hopping

电荷转移中电子耦合偶极子效应的机理研究作为分子内空穴跳跃的光致动力学实现

• 批准号: 1800602
• 负责人: Valentine Vullev
• 金额: $ 43.44万
• 依托单位: University of California-Riverside
• 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=1800602&HistoricalAwards=false
• 关键词: Mechanistic; Studies; Dipole; Effects; Electronic

In this project, funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Valentine Vullev at the University of California, Riverside is developing new classes of synthetic systems to study the influence of dipoles on charge transfer. Charge transfer is among the most fundamental processes, essential for managing energy flow and sustaining life on Earth. Respiration, photosynthesis, batteries, electronic devices and many other intricate components of lives heavily rely on efficient charge-transfer processes. Concurrently, electric dipoles are everywhere, and the localized fields around them can have a profound effect on how charges move. Therefore, it is important to understand how dipoles affect charge transfer, in order to enhance desired forward electron transduction while suppressing undesired processes. Professor Vullev's group is well positioned to provide the highest level of education and training for students, including those underrepresented in science. Outreach activities involving K-12 students are planned. Summer research training, which includes writing scientific papers and producing scientific videos, will be provided for high school students. More specifically, the goal of this project is to explore how dipoles affect electronic coupling in charge-transfer systems in bioinspired molecular electrets, which are systems with ordered electric dipole moments. The research is based on Professor Vullev's discovery that the dipoles of molecular electrets can modulate the delocalization of frontier orbitals and alter donor-acceptor electronic coupling, leading to orders of magnitude changes in the charge-transfer rates. It has three specific aims: (1) determining parameters that govern dipole-modulated electronic coupling; (2) determining the dipole effects on charge transfer occurring via hole-hopping vs. tunneling mechanisms; and (3) determining the effect of radical delocalization on the dynamics of hole hopping.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.

在该项目中，由化学系的化学结构，动力学机制B计划资助，滨江的加州大学的Valentine Vullev教授正在开发新的合成系统类别，以研究偶极子对电荷转移的影响。 电荷转移是最基本的过程之一，对于管理能量流和维持地球上的生命至关重要。呼吸、光合作用、电池、电子设备和生命中许多其他复杂的组成部分都严重依赖于有效的电荷转移过程。同时，电偶极子无处不在，它们周围的局部场对电荷的运动有着深远的影响。 因此，重要的是要了解偶极子如何影响电荷转移，以增强所需的正向电子转导，同时抑制不需要的过程。 Vullev教授的团队有能力为学生提供最高水平的教育和培训，包括那些在科学领域代表性不足的学生。 计划开展涉及K-12学生的外联活动。 将为高中生提供暑期研究培训，包括撰写科学论文和制作科学视频。 更具体地说，该项目的目标是探索偶极子如何影响生物启发分子驻极体中电荷转移系统的电子耦合，生物启发分子驻极体是具有有序电偶极矩的系统。 该研究基于Vullev教授的发现，即分子驻极体的偶极子可以调节前沿轨道的离域，并改变供体-受体电子耦合，导致电荷转移速率的数量级变化。 它有三个具体目标：（1）确定控制偶极调制电子耦合的参数;（2）确定偶极效应对通过空穴跳跃与隧穿机制发生的电荷转移的影响;以及（3）该奖项反映了NSF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进行评估，被认为值得支持的搜索.

项目成果

How does tautomerization affect the excited-state dynamics of an amino acid-derivatized corrole?

• DOI: 10.1007/s11120-021-00824-4
• 发表时间: 2021-05
• 期刊: Photosynthesis research
• 影响因子: 3.7
• 作者: Clark JA;Orłowski R;Derr JB;Espinoza EM;Gryko DT;Vullev VI
• 通讯作者: Vullev VI

What defines biomimetic and bioinspired science and engineering?

• DOI: 10.1515/pac-2021-0323
• 发表时间: 2021-11-01
• 期刊: PURE AND APPLIED CHEMISTRY
• 影响因子: 1.8
• 作者: Rybicka-Jasinska，Katarzyna;Derr，James B.;Vullev，Valentine
• 通讯作者: Vullev，Valentine

Role of intramolecular hydrogen bonds in promoting electron flow through amino acid and oligopeptide conjugates

• DOI: 10.1073/pnas.2026462118
• 发表时间: 2021-03
• 期刊: Proceedings of the National Academy of Sciences
• 作者: Rafał Orłowski;J. Clark;J. Derr;E. M. Espinoza;Maximilian F Mayther;O. Staszewska-Krajewska;J. Winkler;H. Jędrzejewska;A. Szumna;H. Gray;V. Vullev;D. Gryko

How Do Amides Affect the Electronic Properties of Pyrene?

• DOI: 10.1021/acsomega.8b01581
• 发表时间: 2018-10-01
• 期刊: ACS OMEGA
• 影响因子: 4.1
• 作者: Espinoza, Eli M.;Clark, John A.;Vullev, Valentine, I
• 通讯作者: Vullev, Valentine, I

How Do Liquid-Junction Potentials and Medium Polarity at Electrode Surfaces Affect Electrochemical Analyses for Charge-Transfer Systems?

• DOI: 10.1021/acs.jpcb.2c07983
• 发表时间: 2023-02-16
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY B
• 影响因子: 3.3
• 作者: Mayther, Maximillian F.;O'Mari, Omar;Flacke, Paul;Bhatt, Dev;Andrews, Samantha;Vullev, Valentine I.
• 通讯作者: Vullev, Valentine I.