Energy and Electron Transport in pi-Stacked Multichromophoric Assemblies: Global Dynamics from the Gas to Condensed Phase

pi 堆叠多发色团组件中的能量和电子传输：从气相到凝聚相的全局动力学

• 批准号: 1508677
• 负责人: Scott Reid
• 金额: $ 54万
• 依托单位: Marquette University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-09-01 至 2018-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1508677&HistoricalAwards=false
• 关键词: Energy; Electron; Transport; pi; Stacked

In this project funded by the Macromolecular, Supramolecular and Nanochemistry program of the Chemistry Division, Professors Rajendra Rathore and Scott Reid of Marquette University will examine model molecular assemblies that incorporate stacked polycyclic aromatic hydrocarbons. Such interactions are characteristic of many molecular assemblies, including those found in nature (e.g., DNA), and an understanding of the transport of electrons and energy through such assemblies is critical to develop new charge-transfer materials of increased efficiency for applications in photovoltaic devices, molecular electronics, and nanotechnology. To meet this challenge, the synthesis of carefully designed molecular assemblies is carried out, and the assemblies characterized using a variety of experimental strategies based on molecular spectroscopy, supported by computational chemistry. Supramolecular assemblies exploit a variety of covalent and non-covalent scaffolding interactions. Of these, pi-stacking is important. The efficiency of long range charge transfer in the conducting layers of photovoltaic devices is governed not only by the intramolecular electron transport through the backbone of polymers but also by the intermolecular electron transport through bulk material, where the amorphous assembly of pi-conjugated molecules is generally randomized. As cyclophane-like aromatic dimers and their cation radicals represent the simplest fundamental units responsible for charge transport in bulk materials, the design and synthesis of modern organic materials for the emerging area of molecular electronics and nanotechnology demands a thorough understanding of electron and energy-transfer processes in carefully designed cofacially-arrayed molecules. This project addresses fundamental questions concerning the flow of energy and electron transfer in model multichromophoric systems and developes new strategies for exploiting such assemblies as light driven actuators, taking advantage of the molecular rearrangement which accompanies oxidation or electronic excitation. Examining broader impacts, this work informs the design and synthesis of next generation organic materials for applications in the area of molecular electronics and photovoltaics.

在这个由化学系高分子、超分子和纳米化学项目资助的项目中，马凯特大学的 Rajendra Rathore 和 Scott Reid 教授将研究包含堆叠多环芳烃的模型分子组装体。这种相互作用是许多分子组装体的特征，包括自然界中发现的分子组装体（例如 DNA），了解电子和能量通过此类组装体的传输对于开发新的电荷转移材料至关重要，该材料可提高光伏器件、分子电子学和纳米技术应用的效率。 为了应对这一挑战，我们进行了精心设计的分子组装体的合成，并在计算化学的支持下，使用基于分子光谱学的各种实验策略对组装体进行了表征。超分子组装体利用各种共价和非共价支架相互作用。 其中，π 堆叠很重要。光伏器件导电层中长程电荷转移的效率不仅取决于通过聚合物主链的分子内电子传输，还取决于通过本体材料的分子间电子传输，其中π共轭分子的无定形组装通常是随机的。 由于类环芳芳族二聚体及其阳离子自由基代表了散装材料中负责电荷传输的最简单的基本单元，因此分子电子学和纳米技术新兴领域的现代有机材料的设计和合成需要对精心设计的共面排列分子中的电子和能量转移过程有透彻的了解。 该项目解决了有关模型多发色系统中能量流和电子转移的基本问题，并开发了利用光驱动致动器等组件的新策略，利用伴随氧化或电子激发的分子重排。 这项工作考察了更广泛的影响，为分子电子和光伏领域应用的下一代有机材料的设计和合成提供了信息。

项目成果

First Experimental Evidence for the Diverse Requirements of Excimer vs Hole Stabilization in π-Stacked Assemblies

α-堆叠组件中准分子与空穴稳定性不同要求的第一个实验证据

• DOI: 10.1021/acs.jpclett.6b01201
• 发表时间: 2016
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Reilly, Neil;Ivanov, Maxim;Uhler, Brandon;Talipov, Marat;Rathore, Rajendra;Reid, Scott A.
• 通讯作者: Reid, Scott A.

From Wires to Cables: Attempted Synthesis of 1,3,5-Trifluorenylcyclohexane as a Platform for Molecular Cables

从电线到电缆：尝试合成 1,3,5-三芴基环己烷作为分子电缆的平台

• DOI: 10.1021/acs.joc.5b02792
• 发表时间: 2016
• 期刊: The Journal of Organic Chemistry
• 作者: Talipov, Marat R.;Abdelwahed, Sameh H.;Thakur, Khushabu;Reid, Scott A.;Rathore, Rajendra
• 通讯作者: Rathore, Rajendra