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Genevieve Sauve教授正在采用创新的化学设计来创造具有高电子亲和性、优异的电荷传输和低光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。有机芳香族分子，包含π共轭将发展与操纵分子几何的能力，通过与各种金属的螯合。作为π共轭的结果，当施加电压（如晶体管）或光照（如光伏电池）时，这些材料将变得导电。金属在这些材料中的作用不仅是控制分子几何形状，而且还可以调节光电性能、结晶度和溶液可加工性能。解决这些有机半导体的能力将影响可印刷电子工业，提供便携式设备和将太阳能转换为高价值电力的替代方法。该项目如果成功，将提供急需的高性能光电材料，这些材料成本低，使用可持续化学物质和富含地球元素。该研究小组将通过凯斯西大学弗洛拉·斯通·马瑟妇女指导项目中心扩大妇女对科学的参与。该项目将高级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、教育重点和对师徒关系的期望来匹配导师和徒弟。为了扩大少数族裔学生对STEM的参与，将通过美国化学会项目SEED计划招募当地高中生。这项外展活动将在夏季将经济困难的学生安置在研究实验室。该提案将专注于开发新型氮杂二吡咯甲烷（ADP）基配合物，该配合物具有罕见的溶液可加工性，出色的电荷传输，可见光到近红外光谱的吸收以及低合成复杂性。在第一个目标中，将探索非平面ADP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如何影响自组装。这也将为改进非平面系统中的电荷输运建立通用的指导方针。通过优化聚合物供体可以提高有机光伏效率。还将研究平面aza-BODIPY配体以及与IV族元素配位的n2o2型ADP配体。第二个目标将集中于基于aza-BODIPY配体的新型近红外半导体的合成和研究，通过使用非共价构象锁扩展π共轭。这项研究将提供基本的结构-性质关系，有可能改变π共轭分子和聚合物、具有可见近红外吸收的染料、ADP化学和有机电子学领域。这一发现还可能影响包括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在内的应用。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值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.