Contorted and Strained Molecular Nanographenes: Multi-Electron Storage and Reduction-Induced Transformations

在化学系大分子、超分子和纳米化学(MSN)计划的支持下，奥尔巴尼大学的Marina A.Petrukhina教授正在研究新型高度扭曲和扭曲的纳米支架中的电荷转移效应，以促进它们作为储能、导电和量子计算设备中的关键部件。通过系统的研究，该项目旨在提供关于不同拓扑结构的纳米碳主体在逐步化学还原时的多电子存储能力的见解。如果成功，所获得的知识将为设计新的分子和超分子碳材料以及它们各自的电子、磁性和插层性质提供指导原则，用于技术上的重要应用。该项目还将为奥尔巴尼大学的研究生和本科生提供教育和培训机会。学生将接触到广泛的科学，包括有机和有机金属合成，超分子组装，溶液和无溶剂晶体生长，X射线衍射和光谱表征方法。外展和社区参与活动将建立在大学新的新兴技术和创业综合体设施以及专为本科生和高中生设计的暑期研究项目“玩碳球、碗、箍等”的基础上。在这个项目中，将选择各种结构明确、碳骨架扭曲和应变的纳米图形来研究它们的多电子获取和存储能力。利用受控的化学还原方法，系统地评估了负电荷和自旋逐步注入到pi共轭纳米茂体系中的电子和结构后果。更具体地说，将分析分子水平上改变几何结构、官能化和应变的影响，着眼于识别具有增强的电子存储能力的系统。此外，还将研究嵌入奇环的纳米分子在多电子荷电时的结构转变，并将测试创建局部自旋密度和反芳点以诱导特定位置反应的效用。该项目还将探索还原介导的环化方法是否可以用于可控地建立圆周率扩展的纳米碳框架。这项研究旨在解决与石墨材料中的电荷转移相关的基本化学问题，这些问题对下一代光电和能量存储设备的开发非常重要。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。

With the support of the Macromolecular, Supramolecular and Nanochemistry (MSN) program in the Division of Chemistry, Professor Marina A. Petrukhina of the University at Albany is studying charge-transfer effects in the emerging classes of highly warped and twisted nanographene scaffolds to promote their use as critical components in energy storage, conducting and quantum computing devices. Through systematic studies, the project aims to provide insights into multi-electron storage abilities of topologically different nanocarbon hosts upon stepwise chemical reduction. If successful, the knowledge gained will provide guiding principles for the design of new molecular and supramolecular carbon materials and their respective electronic, magnetic, and intercalation properties for technologically important applications. This project will also provide educational and training opportunities for graduate and undergraduate students at the University at Albany. Students will be exposed to a broad range of science including organic and organometallic synthesis, supramolecular assembly, solution and solvent-free crystal growths, X-ray diffraction and spectroscopic characterization methods. Outreach and community engagement activities will build on the new Emerging Technology and Entrepreneurship Complex facility at the university and the summer research program “Playing with Carbon Balls, Bowls, Hoops and More” designed for undergraduate and high school students.In this project, a variety of structurally well-defined nanographenes with contorted and strained carbon frameworks will be selected for investigation of their multi-electron acquisition and storage abilities. Using controlled chemical reduction methods, the electronic and structural consequences of the stepwise injection of negative charge and spin into pi-conjugated nanographene systems will be systematically evaluated. More specifically, the effects of altering geometry, functionalization, and strain at the molecular level will be analyzed with an eye toward identifying systems with enhanced electron storage abilities. Additionally, structural transformations of nanographenes with embedded odd-membered rings upon multi-electron charging will be examined and the utility of creating localized spin-density and anti-aromatic spots for inducing site-specific reactivity will be tested. The project will also probe if the reduction-mediated annulation approach can be utilized for controlled build-up of pi-extended nanocarbon frameworks. This research seeks to address fundamental chemistry questions of relevance to charge transfer in graphitic materials that are important for the development of the next generation of optoelectronic and energy storage devices.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.