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

无机化学、生物无机化学和金属有机化学项目的这一奖项支持韦恩州立大学的克劳迪奥·韦拉尼教授研究过渡金属配位络合物中的氧化还原驱动开关和表面的分子组织。这项工作的目的是通过解决基于溶液的开关和在此类分子中包含两亲性和自组装属性以允许表面沉积之间的差距，使配位化学更接近分子电子学中的器件制造。通过研究正方锥和三角双锥络合物中自由基的形成和稳定，将探索基态转换的新途径。系统的选择灵感来自于在酶的基于自由基的机制中所涉及的五个配位中心中观察到的可逆性和稳定性。这一方法包括电活性配体的设计、络合物的形成、氧化还原、磁性和铁等五配位三价离子的光谱性质的研究等。将评估芳香族基团的影响和多金属/多自由基阵列的形成，并将获得关于自由基稳定/循环和在特殊环境中的弱耦合机制的基本信息。通过Langmuir-Blodgett或自组装薄膜形成的模块化单分子膜的表面沉积新的合成方法将被寻求。这一提议的影响在于将两亲性和自组装特性结合到一类新的基于氧化还原的开关分子中，以便将金属络合物集成到分子电子学中。教育部分致力于提高来自人口群体中代表性不足的初中生在科学领域的接触，并通过在公立学校举办研讨会和在国际学校实验室开展实践工作，解决底特律公立学校系统的科学教师培训问题。非洲裔和拉丁裔学生将被科学和与科学相关的职业所吸引，对科学教师的培训将使这些教师成为更广泛学生的变革工具。

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.