二噻吩并[3,2-b:2\',探索了使用二芳基碘鎓试剂对阳离子苯基磷脂物种的3\'-d]磷孔。测试了多种条件以优化反应,包括溶剂的变化,温度,化学计量,时间,和使用的芳基碘鎓物种。氯化二苯基碘鎓的初始使用导致出乎意料的二噻吩磷Cu(I)氯化物络合物,该络合物在晶体学上进行了表征。或者,在微波条件下在乙醇中使用六氟代磷酸二苯基碘铵导致成功分离了P-芳基化靶标.苯基二噻吩磷物种在溶液中表现出蓝色发光,量子产率为100%,在固态下明显红移。将新物种的光物理和固态组织与相关的甲基同源物进行了比较,显示了磷中心碳基取代基的性质的明显差异,DFT计算也证实了这一点,和固态的超分子组织。
P-Arylation of dithieno[3,2-b : 2\',3\'-d]phosphole toward cationic phenyl phospholium species using diaryliodonium reagents was explored. Multiple conditions were tested to optimize the reaction, including variation of solvent, temperature, stoichiometry, time, and aryliodonium species employed. Initial use of diphenyliodonium chloride led to an unexpected dithienophosphole Cu(I) chloride complex that was characterized crystallographically. Alternatively, the use of diphenyliodonium hexafluorophosphate in ethanol under microwave conditions led to the successful isolation of the P-arylated target. The phenyl dithienophospholium species exhibits blue luminescence with a quantum yield of 100 % in solution that is considerably red-shifted in the solid state. The photophysics and solid-state organization of the new species were compared with those of a related methyl congener, showing distinct differences that are assigned to the nature of the carbon-based substituent at the phosphorus center, which was also confirmed by DFT calculations, and the supramolecular organization in the solid state.