Azadipyrromethene Complexes as a Versatile Platform for Next Generation of Solution-Processable Organic/Inorganic Hybrid Semiconductors

在这个由化学系高分子、超分子和纳米化学计划资助的项目中，凯斯西储大学化学系的Genevive Sauve博士正在开发通过加入金属来制造半导体有机材料的新的合成方法。有机半导体是固体，其组成成分主要由碳和氢原子组成，有时还包括氮、硫和氧。这些材料中的每个碳原子不仅通过单键与其他碳原子相连，而且还通过称为圆周率键的特殊键与其他碳原子相连。交替的pi键使分子(聚合物)能够传导电子。就像用硅制成的传统半导体一样，当人们施加电压(如晶体管)或照射到它们(如光伏电池)时，这些材料可以导电。有机半导体的最大优势是，它们可以像墨水一样打印，从而能够廉价和可扩展地生产电子设备。此外，有机半导体是类似塑料的，可以生产灵活而轻巧的设备，可以用于刚性和重型硅基设备无法使用的地方。然而，基于有机半导体的设备往往比基于传统半导体的设备性能更低。在这项研究中，高度创新和创造性的化学反应被用来通过使用金属来提高有机半导体的性能。将金属添加到这些材料中的目的不仅是为了提供对导电性的额外控制，而且是为了提供对结晶度和溶液加工性能的额外控制。该项目准备的材料预计将影响可印刷电子行业，提供便携设备和将太阳能转换为高价值电力的替代方法。与该项目相关的学生将接触到跨学科研究，并为成为下一代科学家做好准备。YouTube上发布的教育和推广活动针对的是高中生和未被充分代表的群体，因为视频展示了圆周率共轭材料的现实应用。可溶解处理的有机半导体有望给电子和印刷行业带来革命性的变化，但要实现最理想的性能，需要新的创意方法和合成策略。传统的有机半导体设计方法通常依赖于纯平面的pi共轭体系，其光电性质随化学主链、官能团和侧链的性质而调节。为了获得新的功能，这个项目转向有机/无机杂化配位化合物，其中与主基或过渡金属的配位提供了一个额外的工具来调节pi共轭体系的性质，如分子形状、结晶度和光电性质。这项研究利用氮二吡咯亚甲基络合物作为开发下一代可溶液处理的混合半导体的通用平台。这项研究有可能影响圆周率共轭体系、具有可见近红外吸收的染料和有机电子领域。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。

In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Dr. Genevieve Sauve of the Department of Chemistry at Case Western Reserve University is developing new synthetic approaches for making semiconducting organic materials by incorporating metals. Organic semiconductors are solids whose building blocks mainly consist of carbon and hydrogen atoms, and at times nitrogen, sulfur and oxygen. Each carbon atom in these materials is bonded to other carbons not only through single bonds, but also with special bonds called pi-bonds. The alternating pi-bonds enables the molecules (polymers) to conduct electrons. Just like traditional semiconductors made with silicon, these materials can become conductive when one applies a voltage (like in transistors) or shines light on them (like in photovoltaic cells). The big advantage of organic semiconductors is that they can be printed, just like ink, enabling inexpensive and scalable production of electronic devices. In addition, organic semiconductors are plastic-like, producing flexible and lightweight devices that could be used where rigid and heavy silicon-based devices cannot. However, devices based on organic semiconductors tend to have lower performance than devices based on traditional semiconductors. In this research, highly innovative and creative chemical reactions are used to improve the performance of organic semiconductors by using metals. The purpose of adding metals to these materials is to provide additional control over not only electrical conductivity, but also crystallinity and solution processing properties. Materials prepared in this project are expected to impact the printable electronic industry, providing portable devices and alternative ways to convert solar energy to high value electricity. Students associated with this project are exposed to interdisciplinary research and are prepared to be next generation of scientists. Education and outreach activities posted on YouTube target high school students and underrepresented groups as the videos demonstration the real-life applications of pi-conjugated materials.Solution-processable organic semiconductors are poised to revolutionize the electronic and printing industries, but to achieve the most desirable properties, new creative approaches and synthetic strategies are required. Conventional approaches to organic semiconductor design typically rely on purely planar pi-conjugated systems whose opto-electronic properties are tuned with the nature of the chemical backbone, functional groups and side-chains. To access new functionalities, this project turns to hybrid organic/inorganic coordination compounds, where coordination with main group or transition metals provides an additional tool to tune the properties of pi-conjugated systems, such as molecular shape, crystallinity and opto-electronic properties. This research exploits azadipyrromethene complexes as a versatile platform for development of the next generation of solution-processable hybrid semiconductors. The research has the potential to impact the field of pi-conjugated systems, dyes with visible NIR absorption and organic electronics.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.