RUI - Organometallic Porphyrins, BODIPY, and their analogues for light-harvesting and molecular electronics

在这项由化学系化学结构、动态和机理B计划资助的项目中，明尼苏达大学德卢斯分校化学和生物化学系的Viktor N.Nemykin教授将制备和表征有机金属卟啉和其他芳香族大环类似物的供体-受体二联体和供体-触角-受体三联体。Nemykin教授和其他研究小组最近发现，将有机金属取代基引入到卟啉核心中会导致金属-金属长程耦合性质，这对于此类化合物在分子电子学和随机存取存储器件中的应用是必不可少的。研究还表明，有机金属供体-受体二元组和供体-天线-受体三元组可作为染料敏化太阳能电池和有机光伏电池中有效捕光的活性成分。因此，该项目有可能导致制备高效的分子电子学模块。UMD是一个以本科生为主的机构，因此其更广泛的影响包括本科生和研究生的培养(M.S.)学生们。该项目还有助于培养一名优秀的本科生和研究生(M.S.)UMD的化学课程。有机金属化合物，特别是含二茂铁的卟啉及其类似物，表现出丰富的氧化还原和光物理性质。这些体系的氧化还原驱动和/或光致电子或能量转移性质可以通过大环核的修饰或二茂铁基上的取代基来调节。这项拟议的研究将探索合成途径，以制备各种含二茂铁的供体-受体二元体和供体-天线-受体三体，这可能在分子电子学和光收集方面有潜在的应用。对建议化合物的系统研究将使研究人员了解如何以及在多大程度上可以控制氧化电位、稳定性以及光致电子或能量转移性质。要考察的因素包括中心金属离子的性质，过渡金属中心之间的通过键和潜在通过空间距离(S)，几何构型(即轴向配位对赤道配位)，以及大环配体的电子性质。

In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Viktor N. Nemykin of the Department of Chemistry and Biochemistry at University of Minnesota Duluth (UMD) will prepare and characterize donor-acceptor dyads and donor-antennae-acceptor triads of organometallic porphyrins and the other aromatic macrocyclic analogues. Professor Nemykin and other research groups have recently shown that introduction of the organometallic substituents into porphyrin cores results in long-range metal-metal coupling properties, which are essential for application of such compounds in molecular electronics and in random access memory devices. It was also shown that organometallic donor-acceptor dyads and donor-antennae-acceptor triads can be used as active components for effective light-harvesting in dye sensitized solar cells and organic photovoltaics. Therefore, this project potentially could result in the preparation of efficient modules for molecular electronics. UMD is a predominantly undergraduate institution and thus the broader impacts include the training of undergraduate as well as graduate (M.S.) students. The project also contributes to the building of an excellent undergraduate and graduate (M.S.) chemistry program at UMD. Organometallics, in particular ferrocene-containing porphyrins and their analogues, display a rich redox and photophysical properties. Redox-driven and/or photoinduced electron- or energy-transfer properties of these systems can be tuned up by modification of the macrocyclic core or by substituents at the ferrocene group. The proposed research will explore synthetic pathways for the preparation of a variety of ferrocene-containing donor-acceptor dyads and donor-antennae-acceptor triads, which could be potentially used in molecular electronics and light-harvesting. A systematic investigation of the proposed compounds will allow the investigators to understand how and to what extent oxidation potentials, stability, as well as photoinduced electron- or energy-transfer properties can be controlled. The factors to be examined include the nature of the central metal ion, through-bond and potentially through-space distance(s) between the transition-metal centers, the geometry (i.e. axial versus equatorial coordination), and the electronic properties of the macrocyclic ligand.