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

NSF化学部的化学合成项目支持俄勒冈州大学化学生物化学系的Michael Haley教授的研究。Haley教授和他的学生正在准备基于茚并芴骨架或受其启发的分子，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。一旦掌握，Haley小组检查了所有新分子支架的光学和电子特性，重点是将这些材料用于光电子器件，如有机场效应晶体管（OFV）和有机光电子器件（OPV）。该计划的更广泛的影响包括研究生在当地和区域公司的工业实习，研究生与外国合作者的交流，包括主要来自本科院校（PUI）的教授在内的访问科学家的延长逗留，通过促进弱势群体参与的计划，继续让本科生大量参与化学研究。苯型分子在过去十年中经历了复兴，因为化学家已经认识到它们作为有机半导体的潜力，其特征在于低的最高占据分子轨道（HOMO）和最低占据分子轨道（LUMO）能级和小的能隙。 该项目旨在：（1）探索导致不对称衍生化结构的完全共轭茚并芴（IF）核的基本性质和反应性，（2）制备用于详细结构-性质关系研究的衍生化IF和IF-二酮的库，（3）扩展我们的合成路线用于制备和研究未知的完全共轭拓扑结构，例如茚并[1，2-a]芴和引达省二并苯，（4）制备了基于二茚并稠并苯的扩展的醌式IF类似物，并探讨了它们的开壳/双自由基性质。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领域的研究生和本科生研究人员提供了一个良好的培训基地。这些研究为研究人员提供了有机合成，计算化学，X射线晶体学以及电子结构和分子结构之间相互作用的广泛经验。

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.