When is a Pyridine Not a Pyridine? Benzannulated N-Heterocyclic Ligands in Molecular Materials Chemistry

IF 1.1 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
David E. Herbert
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引用次数: 0

Abstract

The C=N bond is a critical structural piece of many N-donor ligand scaffolds and is central to the properties and reactivity of important coordination complexes. For example, C=N units play a key role in the ‘redox non-innocence’ of α-diimine complexes and in making charge-transfer excited-state character available to complexes of N-heterocyclic ligands such as bipyridine. In N-heterocycles like pyridine, benzannulation can be used to extend the conjugated C=N containing π-system to quinoline (2,3-benzopyridine) to acridine (2,3-benzoquinoline). This stabilizes the lowest unoccupied molecular orbital (LUMO) of the molecule and boosts its electron-accepting properties, but the position of the benzannulation matters. For example, phenanthridine (3,4-benzoquinoline), an asymmetric isomer of acridine, bears a similarly electronically accessible extended π-system but more chemically isolated, ‘imine-like’ C=N moiety. This Award Paper presents an overview of our work investigating the impact of such site-selective benzannulation on the chemistry and properties of phenanthridine as a molecule and ligand.
什么时候吡啶不是吡啶?分子材料化学中的苯环n -杂环配体
C=N键是许多N给体配体支架的关键结构片段,对重要配位配合物的性质和反应性至关重要。例如,C=N单元在α-二亚胺配合物的“氧化还原非纯性”中起着关键作用,并使N-杂环配体(如联吡啶)的配合物具有电荷转移激发态特征。在像吡啶这样的N-杂环中,苯并环化可以将共轭的含C=N的π-体系由喹啉(2,3-苯并吡啶)扩展到吖啶(2,3-苯并喹啉)。这稳定了分子的最低未占据分子轨道(LUMO)并提高了其电子接受性能,但苯并环的位置很重要。例如,苯苯三啶(3,4-苯并喹啉)是吖啶的不对称异构体,具有类似的电子可接近的扩展π系统,但在化学上更孤立,类似亚胺的C=N部分。这篇获奖论文概述了我们的工作,研究了这种选择性苯并环化对菲咯啶作为分子和配体的化学和性质的影响。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Canadian Journal of Chemistry
Canadian Journal of Chemistry 化学-化学综合
CiteScore
1.90
自引率
9.10%
发文量
99
审稿时长
1 months
期刊介绍: Published since 1929, the Canadian Journal of Chemistry reports current research findings in all branches of chemistry. It includes the traditional areas of analytical, inorganic, organic, and physical-theoretical chemistry and newer interdisciplinary areas such as materials science, spectroscopy, chemical physics, and biological, medicinal and environmental chemistry. Articles describing original research are welcomed.
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