New Molecular Systems Based on Indenofluorenes and Expanded Quinoidal Analogues: Experimental, Theoretical, and Materials Studies

美国国家科学基金会化学部的化学合成项目支持俄勒冈大学化学与生物化学系Michael Haley教授的研究。Haley教授和他的学生正在制备基于或受茚芴骨架启发的分子，以回答基本的科学问题并探索其材料特性。一个关键的目标是开发简单的合成方法来组装这些强电子接受分子。一旦到手，Haley小组检查了所有新分子支架的光学和电子特性，重点是这些材料在光电器件中的应用，如有机场效应晶体管（ofet）和有机光伏（opv）。该计划的广泛影响包括研究生在当地和地区公司的工业实习，与外国合作者的研究生交换，接待包括主要本科院校（PUIs）教授在内的访问科学家的长期停留，以及通过促进未被充分代表的群体参与的项目，本科生继续大量参与化学研究。在过去的十年中，非苯类分子的研究经历了一次复兴，因为化学家们认识到它们具有低最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）能级和小能量间隙的有机半导体的潜力。本项目旨在：(1)探索全共轭吲哚芴（IF）核心的基本性质和反应性，导致不对称衍生化结构；(2)制备衍生化的IF和IF-二酮文库，用于详细的结构-性质关系研究；(3)扩展我们的合成路线，以制备和研究未知的全共轭拓扑结构，如吲哚[1,2-a]芴和吲哚二烯。(4)制备基于双炔融合烯烯的扩展的quinoidal IF类似物，并探索其开壳/双基性质。在这些研究中开发的分子为实际应用提供了机会，特别是在纳米技术和低成本电子领域。此外，该项目还为基础和应用化学合成方面的研究生和本科生研究人员提供了良好的培训基地。这些研究为研究人员在有机合成，计算化学，x射线晶体学以及电子结构与分子结构之间的相互作用方面提供了广泛的经验。

The Chemical Synthesis Program of the NSF Chemistry Division supports the research of Professor Michael Haley in the Department of Chemistry & Biochemistry at the University of Oregon. Prof. Haley and his students are preparing molecules based on or inspired by the indenofluorene skeleton to answer fundamental scientific questions as well as to explore their materials properties. A key goal is to develop simple synthetic methods for the assembly of these strongly electron-accepting molecules. Once in hand, the Haley group examines the optical and electronic properties of all new molecular scaffolds with an emphasis towards utilization of these materials in optoelectronic devices such as organic field effect transistors (OFETs) and organic photovoltaics (OPVs). The broader impacts of this program include industrial internships for graduate students at local and regional companies, the exchange of graduate students with those of foreign collaborators, the hosting of extended stays of visiting scientists including professors from primarily undergraduate institutions (PUIs), and continued substantial involvement of undergraduates in chemical research via programs which promote participation of underrepresented groups.Research on non-benzenoid molecules has experienced a renaissance over the last decade as chemists have recognized their potential as organic semiconductors characterized by low Highest Occupied Molecular Orbitals (HOMO) and Lowest Unoccupied Molecular Orbitals (LUMO) energy levels and small energy gaps. This projects sets out to: (1) explore the fundamental properties and reactivity of the fully conjugated indenofluorene (IF) core leading to asymmetrically derivatized structures, (2) prepare a library of derivatized IFs and IF-diones for detailed structure-properties relationship studies, (3) extend our synthetic routes for the preparation and study of unknown, fully conjugated topologies such as indeno[1,2-a]fluorenes and indacenodiacenes, and (4) prepare expanded quinoidal IF analogues based diindeno-fused acenes and explore their open shell/biradical character. The molecules developed in these studies present opportunities for practical applications, particularly in the area of nanotechnology and low-cost electronics. Moreover, this project serves as an excellent training ground for graduate and undergraduate researchers in fundamental and applied chemical synthesis. The studies provides the researchers with broad experience in organic synthesis, computational chemistry, x-ray crystallography, and the interplay between electronic structure and molecular architecture.