Earth-Abundant Macrocyclic Metal Complexes for Photoredox Catalysis

光催化剂是影响可再生能源和有机合成化学的有力工具。光催化已经实现了一系列令人印象深刻的小分子和碳官能化反应，并且在这个动态领域中不断发现新的应用。然而，Ru-和Ir-化合物经常用作许多这些过程的光敏剂。大量的研究工作集中在用廉价的、地球上丰富的替代品来取代这些贵金属络合物。我们已经开发了一系列的第一行过渡金属配合物的大环Mabiq配体。M-Mabiq配合物的氧化还原和光化学性质使其成为有前途的光氧化还原催化剂。拟议的研究将侧重于研究一系列单金属和双金属Mabiq络合物的详细光化学性质，以及络合物的更广泛的催化能力。本研究的目的是：1）探索M-Mabiq激发态的性质和性质; 2）探索双重光氧化还原催化的反应范围和机会; 3）合成和研究用于双功能光催化的M-Mabiq配合物。该项目将采用合成，光谱，计算工作和反应性研究的组合。 这项研究将有助于

Photocatalysts are powerful tools for effecting chemistry integral to renewable energy and organic synthesis. Photocatalysis has already enabled an impressive range of small molecule and carbon functionalization reactions, and novel applications are continuously being discovered in this dynamic field. However, Ru- and Ir- compounds, are frequently used as photosensitizers for many of these processes. Significant research efforts have focused on replacing these noble metal complexes with inexpensive, earth-abundant alternatives. We have developed a series of first-row transition metal complexes of the macrocyclic Mabiq ligand. The redox and photochemical properties of the M-Mabiq complexes make them promising photoredox catalysts. The proposed research will focus on studies to examine the detailed photochemical properties of a series of mono- and bi-metallic Mabiq complexes, and the broader catalytic capacity of the complexes. The aim of the research is to 1) probe the nature and properties of the M-Mabiq excited states; 2) explore the reaction scope and opportunities for dual photoredox catalysis; 3) synthesize and study bimetallic Mabiq complexes for bifunctional photocatalysis. The project will employ a combination of synthesis, spectroscopy, computational work and reactivity studies. The research will contribute to t