Synthesis of Triphenylene Derivatives by Rhodium-Catalyzed [2 + 2 + 2] Cycloaddition: Application to the Synthesis of Highly Fluorescent Triphenylene-Based Long Ladder Molecules

The convenient synthesis of substituted tri­phenyl­enes and aza­tri­phenyl­enes has been achieved by the cationic rhodium­(I)/H8-BINAP or BINAP complex-catalyzed [2 + 2 + 2] cycloaddition under mild conditions. Photophysical properties of representative tri­phenyl­enes and aza­tri­phenyl­enes were examined, which revealed that aza­tri­phenyl­enes showed higher fluorescence quantum yields than tri­phenyl­enes. This method was successfully applied to the synthesis of highly fluorescent triphenylene-based long ladder molecules.本研究通过阳离子铑(I)/H8-BINAP或BINAP配合物催化的[2+2+2]环加成反应，在温和条件下成功实现了取代型三亚苯（triphenylene）与氮杂三亚苯（azatriphenylene）的便捷合成。针对代表性三亚苯与氮杂三亚苯的光物理性质开展了系统考察，结果表明氮杂三亚苯的荧光量子产率高于三亚苯。该合成方法已成功应用于高荧光性三亚苯基长梯状分子的合成。