Department of Chemistry and Applied Biosciences, ETH Zurich, 8093, Zurich, Switzerland.
Budapest University of Technology and Economics, Szent Gellért tér 4, 1111, Budapest, Hungary.
Angew Chem Int Ed Engl. 2017 Sep 4;56(37):11226-11231. doi: 10.1002/anie.201705473. Epub 2017 Aug 7.
Phosphorus heterocycles find applications in the synthesis of π-conjugated compounds and as precursors for optoelectronic materials such as organic light-emitting diodes (OLEDs), electronic switches, and transistors. A high-yield, one-pot synthesis of anionic annulated 1,3,4-azadiphospholides from Na(OCP) and 2-chloropyridines is presented. The synthesis proceeds without the use of transition metals and tolerates a wide range of substrates. Cyano-substituted compounds are especially deeply colored and have absorption maxima which range from λ =525 to 596 nm. The optical properties are dominated by the spatial separation of an electron acceptor and donor unit within one molecule (push-pull chromophore). The anionic 1,3,4-azadiphospholides are silylated to neutral siloxy compounds with a strong blue-shifted absorption. This reaction can be reversed by addition of fluoride ions, which allows fluoride ions to be detected in optically low concentrations.
磷杂环化合物在合成π 共轭化合物以及作为光电材料（如有机发光二极管（OLED）、电子开关和晶体管）的前体方面有应用。本文提出了一种从 Na(OCP)和 2-氯吡啶出发，高产率、一锅法合成阴离子稠合 1,3,4-氮杂膦的方法。该合成过程无需使用过渡金属，且能耐受多种底物。氰基取代的化合物颜色特别深，其吸收最大值范围为 λ =525 至 596nm。光学性质主要由一个分子内电子给体和受体单元的空间分离（推-拉生色团）决定。阴离子 1,3,4-氮杂膦被硅烷基化为具有强蓝移吸收的中性硅氧基化合物。通过添加氟离子可以使该反应逆转，从而可以在低浓度的光学条件下检测氟离子。
