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

在化学系化学结构、动力学机制B项目资助的本课题中，明尼苏达大学杜卢斯（UMD）化学和生物化学系的Nemykin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-天线-受体三联体。 Nemykin教授和其他研究小组最近表明，将有机金属取代基引入卟啉核中会产生长程金属-金属耦合特性，这对于此类化合物在分子电子学和随机存取存储器器件中的应用至关重要。 研究还表明，有机金属给体-受体二元组和给体-天线-受体三元组可以用作染料敏化太阳能电池和有机光致发光材料中有效捕光的活性组分。因此，该项目可能导致制备用于分子电子学的有效模块。UMD是一个以本科为主的机构，因此更广泛的影响包括本科和研究生（MS）的培训。学生 该项目还有助于建设一个优秀的本科生和研究生（硕士）。化学实验室有机金属化合物，特别是含二茂铁的卟啉及其类似物，显示出丰富的氧化还原和物理性质。 这些系统的氧化还原驱动和/或光诱导的电子或能量转移性质可以通过修饰大环核或通过二茂铁基团上的取代基来调节。 拟议的研究将探索制备各种含二茂铁的供体-受体二元组和供体-天线-受体三元组的合成途径，这些三元组可能用于分子电子学和光捕获。 对所提出的化合物进行系统的研究将使研究人员能够了解如何以及在多大程度上控制氧化电位、稳定性以及光诱导电子或能量转移特性。 要检查的因素包括中心金属离子的性质，通过键和潜在的通过空间之间的距离（S）的过渡金属中心，几何形状（即轴向与赤道配位），和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.