Department of Chemical Science and Engineering, School of Material and Chemical Technology, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro, Tokyo, 152-8552, Japan.
Chem Rec. 2018 Apr;18(4):445-458. doi: 10.1002/tcr.201700052. Epub 2017 Nov 14.
Installing π-functional substituents on the skeletal phosphorus atoms of the air-tolerant 1,3-diphosphacyclobutane-2,4-diyl unit are promising for tuning the open-shell singlet P-heterocyclic chromophore. The sterically encumbered 1,3-diphosphaCycloButen-4-yl Anion (CBA), generated from the phosphorus-carbon triple bond, was available for the regioselective arylation via nucleophilic aromatic substitution (S Ar) reaction, addition to arynes, and single-electron transfer (SET) process affording the corresponding P-arylated 1,3-diphosphacyclobutane-2,4-diyls. The photo-absorption and redox properties correlated with the effects of the aryl substituents on the 1,3-diphosphacyclobutane-2,4-diyl unit. The X-ray analyses enabled not only to discuss the metric parameters but also to visualize the radicalic electrons via the electron-density distribution analysis. The electron-donating character of the P-heterocyclic chromophores induced the p-type semiconductor behavior. Detection of hydrogen fluoride via formation of the 1λ ,3λ -diphosphete derivative was also developed.
在耐空气的 1,3-二磷杂环丁烷-2,4-二基单元的骨架磷原子上安装π-功能取代基，是调节开壳单重态 P-杂环发色团的一种很有前途的方法。从磷-碳三键生成的空间位阻较大的 1,3-二磷杂环丁烯-4-基阴离子（CBA），可通过亲核芳香取代（S Ar）反应、与芳炔加成和单电子转移（SET）过程进行区域选择性芳基化，得到相应的 P-芳基化 1,3-二磷杂环丁烷-2,4-二基。光吸收和氧化还原性质与 1,3-二磷杂环丁烷-2,4-二基单元上芳基取代基的影响相关。X 射线分析不仅能够讨论度量参数，还能够通过电子密度分布分析来可视化自由基电子。P-杂环发色团的供电子特性诱导了 p 型半导体行为。还开发了通过形成 1λ,3λ -二磷杂膦衍生物来检测氟化氢的方法。
