Larrañaga Olatz, Romero-Nieto Carlos, de Cózar Abel
Departamento de Química Orgánica I Facultad de Química, Universidad del País Vasco and Donostia International Physics Center (DIPC), P.K. 1072, San Sebastián-Donostia, E-20018, Spain.
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, Heidelberg, 69120, Germany.
Chemistry. 2019 Jul 5;25(38):9035-9044. doi: 10.1002/chem.201900225. Epub 2019 Jun 11.
The development of π-extended phosphorus heterocycles has been rapidly increasing because of their unique optoelectronics properties, which are very often considered to be a consequence of special hyperconjugative interactions. However, the latter interactions have primarily been investigated within the five-membered species, phospholes, and they are often conceptually extrapolated to the rest of π-extended phosphorus heterocycles (including six-membered P-heterocycles) despite evident structural differences. Herein, we report, for the first time, a detailed investigation that sheds light on the hyperconjugative effects of a series of phosphorus heterocyclic systems by means of EDA and NBO calculations within a DFT framework. Our results lay the foundations for the future design of π-extended phosphorus heterocycles with improved optoelectronics properties.
由于其独特的光电性质，π-扩展磷杂环的发展迅速增长，这种性质常常被认为是特殊超共轭相互作用的结果。然而，后者的相互作用主要是在五元物种磷杂环内进行研究，尽管存在明显的结构差异，但它们常常在概念上外推到其余的π-扩展磷杂环（包括六元P-杂环）。在此，我们首次报告了一项详细研究，该研究通过在DFT框架内进行EDA和NBO计算，揭示了一系列磷杂环系统的超共轭效应。我们的结果为未来设计具有改进光电性质的π-扩展磷杂环奠定了基础。
