Bioinspired Complexes of Asymmetric Ligands as Redox-responsive Precursors toward Surface-based Molecular Electronics

这个无机、生物无机和有机金属化学项目的奖项支持韦恩州立大学Claudio Verani教授对过渡金属配位配合物中氧化还原驱动的开关和表面分子组织的研究。这项工作的目的是通过解决基于溶液的开关和在这些分子中包含两亲性和自组装性质之间的差距，从而使配位化学更接近分子电子学中的器件制造，从而允许表面沉积。通过研究方锥体和三角双锥体配合物中自由基的形成和稳定，将探索基态开关的新方法。选择系统的灵感来自于在酶的自由基机制中观察到的五坐标中心的可逆性和稳定性。这种方法包括电活性配体的设计、络合物的形成、五坐标三价离子（如铁）的氧化还原、磁性和光谱性质的研究等。芳香族基团和多金属/多自由基阵列形成的影响将被评估，并将获得关于自由基稳定/循环和弱耦合在异常环境中的机制的基本信息。新的合成方法将用于通过Langmuir-Blodgett或自组装膜形成获得的模块化单层的表面沉积。该提议的影响在于将两亲性和自组装性质结合到一类新的基于氧化还原的开关分子中，以便将金属配合物整合到分子电子学中。教育部分努力提高来自代表性不足的人口群体的初中生和高中生在科学方面的曝光率，并通过在公立学校举办研讨会和在PI实验室的实践工作来解决底特律公立学校系统科学教师的培训问题。非裔美国人和拉丁裔学生将被科学和与科学有关的职业所吸引，对科学教师的培训将使这些教师成为更广泛的学生变革的工具。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Prof. Claudio Verani at Wayne State University to study redox-driven switching in transition-metal coordination complexes and molecular organization on surfaces. The work is aimed at moving coordination chemistry closer to device fabrication in molecular electronics by addressing a gap between solution-based switching and the inclusion of amphiphilic and self assembling properties in such molecules to allow for surface deposition. New approaches for ground-state switching will be explored by investigating radical formation and stabilization in square pyramidal and trigonal bipyramidal complexes. The choice of systems is inspired by the reversibility and stability observed in five-coordinate centers involved in radical-based mechanisms in enzymes. This approach includes the design of electroactive ligands, complex formation, the study of redox, magnetic, and spectroscopic properties of five-coordinate trivalent ions such as iron, among others. The influence of aromatic groups and the formation of multimetal/multiradical arrays will be assessed, and fundamental information will be obtained regarding the mechanisms of radical stabilization/cycling and weak coupling in unusual environments. New synthetic methodologies will be pursued for surface deposition based on modular monolayers obtained via Langmuir-Blodgett or self-assembled film formation.The impact of this proposal lies in incorporating amphiphilic and self-assembling properties in a new class of redox-based switching molecules in order to integrate metal complexes into molecular electronics. The educational component strives to enhance the exposure of middle- and high school students from underrepresented demographic groups in the sciences, and addresses the training of science teachers from the Detroit Public School system by means of seminars at public schools and hands-on work in the PI's lab. African-American and Latino students will be attracted to the sciences and science-related careers, and the training of science teachers will enable these instructors to become instruments of change for a wider range of students.