Collaborative Research: Hydrazone-Based Solid-State Light Emitters

非技术摘要用高效的固态照明设备取代广泛使用且效率极低的白炽灯和紧凑型荧光灯，可以极大地降低我们的家庭总能耗和二氧化碳排放量。该项目正在开发两种类型的固态发光器，以解决与基于有机材料的固态发光器相关的多种缺点。为了实现这一目标，研究小组正在利用实验和计算技术推进对基于肼类固态发光体的分子水平的理解。两名首席调查人员积极参与教育和外联活动，为NH和VT的贫困大学预科学生提供有意义的学习机会，留住他们所在机构已经在化学管道中的学生，并通过非正式的科学教育活动吸引公众参与。这些研究和推广活动得到了材料研究部的固体和材料化学计划以及化学部的微分子、超分子和纳米化学计划的支持。技术摘要这一合作研究项目利用有机化学和物理化学的工具，促进对基于肼的材料两个显著的光物理性质的基本了解，即聚集诱导发射(AIE)和宽带荧光。BF2-肼(BODIHY)染料带来了固态光(SSL)发射体领域的范式转变，因为这些分子在固态下表现出AIE，尽管分子间存在pi-pi相互作用，似乎有利于猝灭。本文研究的另一类基于肼的材料是三唑并吡啶(TOP)盐，它们是具有大斯托克斯位移和宽荧光带宽的蓝光发射材料，这两种特性在先进能源应用中具有巨大的潜在价值。达特茅斯学院的研究小组使用一种有效的合成方法来准备各种BODIHY和TOP染料的文库，用于结构-性质分析。这些BODIHY和TOP染料的光物理性质在溶液和固体中都得到了广泛的表征，主要是使用电子吸收和荧光光谱。此外，佛蒙特州大学的研究小组利用电子结构计算来阐明基于肼的染料的光物理机制，并对其荧光特性做出先验预测，以加速发现和开发可轻松部署和集成到SSL应用中的新型高效固态发射器。最终，该项目在有机化学和物理化学领域创造了新的基础知识，这对材料和超分子化学社区具有重要价值。

Non-Technical AbstractReplacing widely used and highly inefficient incandescent bulbs and compact fluorescent lamps with efficient solid-state light devices can drastically reduce our total domestic energy consumption and CO2 production. This project is developing two classes of solid-state light emitters to address multiple drawbacks associated with organic material-based solid-state light emitters. To accomplish this goal, the research team is advancing the molecular level understanding of hydrazone-based solid-state light emitters using experimental and computational techniques. The two lead investigators are actively involved in educational and outreach activities that provide meaningful learning opportunities for underprivileged pre-college students in NH and VT, retain students already in the chemistry pipeline at their institutions, and engage the general public through informal science education activities. These research and outreach activities are supported by the Solid State and Materials Chemistry program in the Division of Materials Research as well as the Marcromolecular, Supramolecular, and Nanochemistry program in the Division of Chemistry.Technical AbstractThis collaborative research project employs the tools of organic and physical chemistry to advance fundamental understanding of two remarkable photophysical properties of hydrazone-based materials, namely, aggregation induced emission (AIE) and broad fluorescent bandwidths. BF2-hydrazone (BODIHY) dyes have brought about a paradigm shift in the field of solid-state light (SSL) emitters as these molecules exhibit AIE in the solid-state despite the presence of intermolecular pi-pi interactions that would seem to favor quenching. The other family of hydrazone-based materials investigated here, triazolopyridinium (TOP) salts, are blue light emitting materials with large Stokes shifts and broad fluorescent bandwidths, two properties of great potential value in advanced energy applications. The research team at Dartmouth College uses an efficient synthetic approach to prepare diverse libraries of BODIHY and TOP dyes for structure-property analyses. The photophysical properties of these BODIHY and TOP dyes are extensively characterized, both in solution and the solid-state, primarily using electronic absorption and fluorescence spectroscopies. In addition, the research team at the University of Vermont utilizes electronic structure calculations to elucidate the photophysical mechanisms of hydrazone-based dyes, and make a priori predictions regarding their fluorescent properties to expedite the discovery and development of new and efficient solid-state emitters that can be easily deployed and integrated into SSL applications. Ultimately, this project creates new, fundamental knowledge in the fields of organic and physical chemistry, which is of significant value to the materials and supramolecular chemistry communities.