Synthesis of Main Group Compounds and Materials with Novel Structures and Optoelectronic Properties

具有新颖结构和光电性能的主族化合物和材料的合成

• 批准号: 2246810
• 负责人: John Protasiewicz
• 金额: $ 59万
• 依托单位: Case Western Reserve University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-06-15 至 2026-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2246810&HistoricalAwards=false
• 关键词: Synthesis; Main; Group; Compounds; Materials

With the support of the Chemical Synthesis program of the Division of Chemistry, Professor John Protasiewicz and his students at the Department of Chemistry at Case Western Reserve University are preparing compounds with P=C-containing extended pi-electron systems. The inclusion of P=C units permits the optical and electronic properties of the material to be tuned in order to maximize the behavior of the material. A motivation for these studies is a need for economical means to manufacture highly efficient lighting and displays. Methods that utilize inexpensive and abundant elements and ones that minimize the formation of wasteful and toxic byproducts are especially attractive. This project envisions the preparation of low cost/lightweight/processable plastics and materials related to light emitting technology. Examples, include polymers, molecular electronics, light emitting diodes, photovoltaics, and flexible electronics. The students trained and educated as part of this research program are being prepared to enter tomorrow's skilled workforce in industry and education. In addition to the technical broader impacts related to advanced manufacturing, Professor Protasiewicz will co-organize and run programs directed at raising awareness of mental health issues among graduate students and faculty.Reactive main group systems will be synthesized and their photophysical properties interrogated to advance and create new paradigms in main group photophysical chemistry. This work explores several interconnected research threads, inspired from previous studies on luminescent 1,3-benzoxaphospholes and 1,3-benzazaphospholes. A new class of photoluminescent compounds (phospha-azulenes) bearing P=C bonds will be prepared to display fluorescence from the S2 (not S1) excited state, thus breaking Kasha's rule. Anti-Kasha compounds are rare and have desirable photophysical properties. Unconventional hydrogen bonding between N-heterocyclic carbenes and fluorescent secondary amines will be exploited to develop the supramolecular chemistry of dicarbenes that can undergo hydrogen bonding to a fluorophores containing two NH functional groups, which will offer new opportunities to develop materials that could act as turn-on fluorescent sensors for select applications. Previous studies also uncovered an unusual reaction that converts ortho-phosphinophenol to benzodioxaphosphole. This process involves removing 6 hydrogen atoms and making new PP and PO bonds. This process will be extended to other types of bonds and and attempts will be made to make the process catalytic. The metal-free systems to be developed in this research move away from previously reported strategies based on expensive and/or toxic transition metals and concentrates on elements that are less toxic and more earth abundant. Combined, these efforts aim to advance and showcase the advantages that main group elements can offer to the greater field of optoelectronic and structural materials.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.

在化学系化学合成项目的支持下，凯斯西储大学化学系的John Protasiewicz教授和他的学生正在制备含有P=C的扩展π电子系统的化合物。包含 P=C 单元可以调节材料的光学和电子特性，以最大限度地提高材料的性能。这些研究的动机是需要经济的手段来制造高效的照明和显示器。利用廉价且丰富的元素以及最大限度地减少浪费和有毒副产品形成的方法尤其有吸引力。该项目设想制备低成本/轻质/可加工的塑料和与发光技术相关的材料。例子包括聚合物、分子电子学、发光二极管、光伏和柔性电子学。作为该研究计划的一部分接受培训和教育的学生正在准备进入未来工业和教育领域的熟练劳动力。除了与先进制造相关的更广泛的技术影响外，Protasiewicz 教授还将共同组织和运行旨在提高研究生和教师对心理健康问题的认识的项目。反应性主族系统将被合成，其光物理特性将被研究，以促进和改善心理健康问题。创建主族光物理化学的新范例。 这项工作探索了几个相互关联的研究线索，其灵感来自于之前对发光 1,3-苯并氧磷和 1,3-苯并氮杂磷的研究。 将制备一类带有 P=C 键的新型光致发光化合物（磷光甘菊烯），以显示来自 S2（而非 S1）激发态的荧光，从而打破 Kasha 规则。 抗卡莎化合物很罕见，并且具有理想的光物理特性。 N-杂环卡宾和荧光仲胺之间的非常规氢键将被用来开发二卡宾的超分子化学，该化学可以与含有两个NH官能团的荧光团发生氢键结合，这将为开发可充当转接剂的材料提供新的机会。适用于特定应用的荧光传感器。 之前的研究还发现了一种不寻常的反应，将邻膦苯酚转化为苯并二氧磷。 该过程涉及去除 6 个氢原子并形成新的 PP 和 PO 键。 该过程将扩展到其他类型的债券，并将尝试使该过程具有催化作用。本研究中开发的无金属系统摆脱了先前报道的基于昂贵和/或有毒过渡金属的策略，并专注于毒性较小且地球资源丰富的元素。 这些努力结合在一起，旨在推进和展示主要组元素可以为更广泛的光电和结构材料领域提供的优势。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进行评估，被认为值得支持审查标准。