Redox, Electronic, and Rectifying Response of Five- and Six-coordinate Metallosurfactants in Solution, as Films, and on Electrodes

在这个由化学系大分子、超分子和纳米化学项目资助的项目中，Cláudio N. Verani教授和他在底特律韦恩州立大学的研究小组正在研究能够作为二极管进行电流整流的金属基分子。整流，或定向电流从电极A流向电极B（而不是从B返回到A），是交流电转换为直流电的基础，对于电子数据计算是绝对必要的。这一跨学科的建议旨在提高我们对金属表面活性剂用于分子二极管的基本理解。更广泛的影响包括向四年级和五年级学生推广科学，以及努力促进拉丁裔学生参与STEM研究。Verani及其合作者正在研究金属表面活性剂的氧化还原、电子和整流行为，包括溶液和沉积在金电极上的Langmuir-Blodgett单层膜。因此，这个跨学科项目的重点是通过电流/电位（I/V）曲线的不对称性来测量两亲性配位配合物对电流整流组件的使用，旨在了解(I)金属表面活性剂中的主要整流机制；（ii）金属基单占分子轨道（SOMOs）中电子转移中介的可能性；（iii）金属在配体中心最低未占据和最高已占据分子轨道（LUMOS和HOMOs）之间进行电子转移中介的可行性；（四）金属表面活性剂取向在整流机理中的作用；(v)金属表面活性剂几何形状对观察到的对称传导、单分子或不对称整流或绝缘的影响。这项研究是多方面的，包括在合成方法、电化学、光谱、计算、等温压缩和显微镜方法方面取得进展的努力。

In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program of the Division of Chemistry, Professor Cláudio N. Verani and his research group at Wayne State University in Detroit are studying metal-based molecules able to act as diodes for electric current rectification. Rectification, or directional current flow from an electrode A to an electrode B (but not from B back to A) is fundamental to the conversion of alternating into direct current, and is absolutely necessary for electronic data computation. This interdisciplinary proposal seeks to enhance our fundamental understanding on the use of metallosurfactants for molecular diodes. Broader impacts include scientific outreach to fourth and fifth graders and effort to promote Latino-student inclusion in STEM research.Verani and collaborators are studying the redox, electronic, and rectifying behavior of metallosurfactants, both in solution and as Langmuir-Blodgett monolayer films deposited onto gold electrodes. Therefore, this interdisciplinary program focuses on the use of amphiphilic coordination complexes towards current-rectifying assemblies as measured by the asymmetry of current/potential (I/V) curves aiming to understand (i) the predominant rectification mechanisms in metallosurfactants; (ii) the possibility of electron-transfer mediation in metal-based singly occupied molecular orbitals (SOMOs); (iii) the viability of electron transfer mediation by metals between ligand-centered lowest unoccupied & highest occupied molecular orbitals (LUMOS & HOMOs); (iv) the role of metallosurfactant orientation in the mechanism of rectification; (v) the influence of the metallosurfactant geometry in observed symmetric conduction, unimolecular or asymmetric rectification, or insulation. This research is multi-faceted, incluidng efforts to make strides in synthetic methodologies, and in electrochemical, spectroscopic, computational, isothermal compression, and microscopy methods.