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Covalently Linked 5,15-Diazaporphyrin Dimers: Promising Scaffolds for a Highly Conjugated Azaporphyrin π System

机译:共价连接的5,15-重氮卟啉二聚体:高度共轭的重氮卟啉π系统的有希望的支架。

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摘要

The first examples of β–β directly linked, acetylene- bridged, and butadiyne-bridged 5,15-diazaporphyrin dimers have been prepared by palladium-catalyzed coupling reactions of nickel(II) and copper(II) complexes of 3-bromo- 10,20-dimesityl-5,15-diazaporphyrin (mesityl=2,4,6-trimethylphenyl). The effects of the linking modes and meso-nitrogen atoms on the structural, optical, electrochemical, and magnetic properties of the distributed p systems were investigated by using X-ray crystallography, UV/Vis absorption spectroscopy, DFT calculations, cyclic voltammetry, and ESR spectroscopy. Both the electronic and steric effects of the meso-nitrogen atoms play an important role in the highly coplanar geometry of the directly linked dimers. The direct β–β linkage produces enhanced p conjugation and electronspin coupling between the two diazaporphyrin units.
机译:通过钯催化3-溴-10的镍(II)和铜(II)配合物的偶联反应,可以制备直接连接,乙炔桥和丁二炔桥的5,15-二氮杂卟啉二聚体的第一个β-β实例。 ,20-二甲磺酰基-5,15-二氮杂卟啉(甲磺酰基= 2,4,6-三甲基苯基)。通过使用X射线晶体学,UV / Vis吸收光谱,DFT计算,循环伏安法和ESR,研究了连接模式和中氮原子对分布式p系统的结构,光学,电化学和磁性的影响。光谱学。中氮原子的电子和空间效应在直接连接的二聚体的高度共面几何结构中都起着重要作用。直接的β-β键在两个diazaporphyrin单元之间产生增强的p共轭和电子自旋耦合。

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