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

CAS：通过分子设计和结构性能研究推进氮杂二吡咯亚甲基配合物的化学和应用

• 批准号: 2203595
• 负责人: Genevieve Sauve
• 金额: $ 50万
• 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: 2022
• 资助国家: 美国
• 起止时间: 2022-07-01 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2203595&HistoricalAwards=false
• 关键词: CAS; Advancing; Chemistry; Applications; Azadipyrromethene

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.

在化学系的大分子，超分子和纳米化学计划的支持下，凯斯西部储备大学的Genevieve Sauve教授正在采用创新的化学设计来创建具有高成本的可溶液可加功能的半导体，具有高电子亲和力，高电荷运输，出色的电荷运输和低光学差距。 这些功能对于各种有机电子和太阳能转换应用至关重要。 将开发包含PI缀合的有机芳香族分子，具有通过用多种金属螯合来操纵分子几何形状的能力。 由于PI缀合的结果，当施加电压（如在晶体管中）或在其上照明（如光伏电池中）时，这些材料将成为导电性。这些材料中金属的目的不仅是控制分子几何形状，而且还要调整光电特性，结晶度和溶液处理性能。解决这些有机半导体的解决方法的能力将影响可打印的电子行业，提供便携式设备和替代方法，以将太阳能转换为高价值的电力。如果成功的话，该项目将提供低成本和使用可持续化学和地球丰富元素的急需的高性能光电材料。研究小组将通过凯斯·西大学（Case Western University）的弗洛拉·斯通马瑟（Flora Stone Math）女性指导计划拓宽女性参与科学的参与。该计划将高级本科生或高级博士生与专业人士配对，以培养社区感并提供专业榜样。导师与基于职业兴趣，教育重点和指导关系期望的受训者相匹配。为了扩大少数族裔学生参与STEM的参与，将通过美国化学学会项目种子计划招募当地高中生。 这种外展活动将在夏季将经济不利的学生置于研究实验室。 该提案将集中于新型硫基丙烯（ADP）基于基于溶液的加工性，出色的电荷传输，可见度对NIR光谱的吸收和低合成复杂性的罕见组合的复合物的发展。在第一个目标中，将探索非平面锌（II）复合物的二氟萘基和三氟甲基功能化，以进一步了解偶极矩强度和方向如何自组装。这还将建立一般的准则，以改善非平面系统中的电荷运输。通过优化聚合物供体，将提高有机光伏效率。 平面AZA-Bodipy配体以及与IV组元素协调的N2O2型ADP配体。第二个目标将通过使用非共价构象锁扩展Pi-concodation来关注基于AZA-Bodipy配体的新型NIR半导体的合成和研究。这项研究将提供基本的结构特性关系，这些关系有可能改变偶联分子和聚合物的领域，具有可见NIR吸收，ADP化学和有机电子产品的染料。这些发现还可能影响包括NIR光电探测器和传感器，生物成像，太阳能转化和光催化的应用。该奖项反映了NSF的法定任务，并被认为是通过基金会的智力优点和更广泛的影响来通过评估来获得支持的。