CAS: Advancing the Chemistry and Applications of Azadipyrromethene-based Complexes through Molecular Design and Structure-property Studies

在化学系大分子、超分子和纳米化学项目的支持下，凯斯西储大学的Genevive Sauve教授正在利用创新的化学设计来创造具有高电子亲和力、出色的电荷传输和低光学带隙的低成本溶液可加工半导体。这些特性对于各种有机电子和太阳能转换应用至关重要。含有圆周率共轭的有机芳香族分子将被开发出能够通过与各种金属的螯合来操纵分子几何结构的能力。作为圆周率共轭的结果，当人们施加电压(如晶体管)或照射到它们上(如光伏电池)时，这些材料就会导电。金属在这些材料中的用途不仅仅是控制分子的几何形状，还可以调节光电性能、结晶度和溶液的可加工性。溶液处理这些有机半导体的能力将影响可印刷电子行业，提供将太阳能转换为高价值电力的便携式设备和替代方法。该项目如果成功，将提供获得急需的低成本高性能光电材料的途径，这些材料使用可持续的化学物质和丰富的稀土元素。研究小组将通过凯斯西大学的弗洛拉·斯通女性指导中心项目扩大女性对科学的参与。该项目将高水平本科生或高级博士生与专业人士配对，以培养社区意识并提供专业榜样。根据职业兴趣、教育重点和对指导关系的期望，导师与被辅导者匹配。为了扩大少数族裔学生在STEM的参与，将通过美国化学学会项目SEED计划招募当地高中生。这项外展活动将在暑假期间将经济困难的学生安排到研究实验室。这项建议将专注于开发基于氮杂二吡咯亚甲基(ADP)的新型配合物，这些配合物具有溶液可加工性、出色的电荷传输、在可见光到近红外光谱中的吸收以及低合成复杂性的罕见组合。在第一个目标中，我们将探索ADP非平面锌(II)配合物的二氟化萘和三氟甲基功能化，以进一步了解偶极矩强度和方向对自组装的影响。这也将建立普遍的指导方针，以改善非平面系统中的电荷传输。有机光伏效率将通过优化聚合物给体来提高。平面氮杂-BODIPY配体以及与IV族元素配位的N2O2型ADP配体也将被研究。第二个目标将集中在通过使用非共价构象锁扩展pi-共轭来合成和研究基于aza-BODIPY配体的新型近红外半导体。这项研究将提供基本的结构-性质关系，这些关系有可能改变PI共轭分子和聚合物、具有可见近红外吸收的染料、ADP化学和有机电子领域。这些发现还可能影响到近红外光电探测器和传感器、生物成像、太阳能转换和光催化等应用。这一奖项反映了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。

With the support of the Macromolecular, Supramolecular and Nanochemistry program in the Division of Chemistry, Professor Genevieve Sauve of Case Western Reserve University is employing innovative chemical design to create low-cost solution-processable semiconductors with high electron affinity, excellent charge transport and low optical gap. These features are critical for a variety of organic electronic and solar energy conversion applications. Organic aromatic molecules that contain pi-conjugation will be developed with the ability to manipulate the molecular geometry by chelation with a variety of metals. As a result of pi-conjugation, these materials will become conductive when one applies a voltage (like in transistors) or shine light on them (like in photovoltaic cells). The purpose of metals in these materials is not only to control the molecular geometry, but also to tune optoelectronic properties, crystallinity and solution processable properties. The ability to solution-process these organic semiconductors will impact the printable electronic industry, providing portable devices and alternatives ways to convert solar energy to high value electricity. This project, if successful, will provide access to much needed high-performance optoelectronic materials that are low-cost and use sustainable chemistries and earth abundant elements. The research team will broaden participation of women in science through the Flora Stone Mather Center for Women Mentoring Program at Case Western University. This program pairs upper-level undergraduate students or advanced doctoral students with professionals to foster a sense of community and provide professional role models. Mentors are matched with mentees based on career interests, educational focus, and mentoring relationship expectations. To broaden participation of minority students in STEM, local high school students will be recruited through the American Chemical Society project SEED program. This outreach activity will place economically disadvantaged students into research laboratories during the summer. This proposal will focus on the development of novel azadipyrromethene (ADP)-based complexes that have the rare combination of solution processability, excellent charge transport, absorption in the visible to NIR spectrum, and low synthetic complexity. In the first objective, difluorinated naphthyls and trifluoromethyl functionalization of non-planar zinc(II) complexes of ADP will be explored to further the understanding of how the dipole moment strength and direction effects self-assembly. This will also establish generalized guidelines to improve charge transport in non-planar systems. Organic photovoltaic efficiency will be increased by optimizing the polymer donor. Planar aza-BODIPY ligands as well as N2O2-type ADP ligands coordinated with group IV elements will also be researched. The second objective will focus on the synthesis and studies of novel NIR semiconductors based on aza-BODIPY ligands by extending pi-conjugation using noncovalent conformational locks. This research will provide fundamental structure-property relationships that have the potential to transform the field of pi-conjugated molecules and polymers, dyes with visible NIR absorption, ADP chemistry, and organic electronics. The findings could also impact applications including NIR photodetectors and sensors, bioimaging, solar energy conversion and photocatalysis.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.