A rational and highly efficient method to access lithium 2,3,4,5-tetraphenylphospholide directly from white phosphorus, diphenylacetylene and lithium has been developed. This novel, convenient synthetic route has allowed the incorporation of various chiral substituents into 2,3,4,5-tetraarylphospholes. The spatial and electronic structures of the obtained novel enantiopure phospholes, their oxides and sulfides have been characterized both experimentally (single-crystal X-ray diffraction) and computationally (DFT). The experimental vibrational Raman spectra and electronic absorption and emission spectra of the synthesized compounds have been interpreted using quantum chemical calculations. A moderate impact of the substituent at the P-atom on the photophysical properties of the phospholes was demonstrated both experimentally and theoretically, while the oxidation/thionation of the phosphorus center was shown to influence remarkably both absorption and emission spectral characteristics. The latter effect is ascribed to the increase of conjugation strength of the oxidized/thionated species with exocyclic Ph rings.

中文翻译：

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新型对映纯单磷脂：合成，空间和电子结构，光物理特性和共轭效应†

已经开发出一种合理，高效的方法，可直接从白磷，二苯乙炔和锂中获取2,3,4,5-四苯基磷化锂。这种新颖，方便的合成途径已允许将各种手性取代基并入2,3,4,5-四芳基磷脂中。获得的新型对映纯磷脂的空间和电子结构，其氧化物和硫化物已通过实验（单晶X射线衍射）和计算（DFT）进行了表征。已使用量子化学计算解释了合成化合物的实验振动拉曼光谱以及电子吸收和发射光谱。取代基对P的中等影响在理论上通过实验证明了磷原子的光物理性质，而磷中心的氧化/硫磺化则显着影响吸收和发射光谱特性。后一种效应归因于具有环外Ph环的氧化/亚硫离子种类的结合强度的增加。