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首页> 外文期刊>Chemistry: A European journal >3,4-Dithiaphosphole and 3,3′,4,4′-tetrathia-1,1′- biphosphole π-conjugated systems: S makes the impact
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3,4-Dithiaphosphole and 3,3′,4,4′-tetrathia-1,1′- biphosphole π-conjugated systems: S makes the impact

机译：3,4-Dithiaphosphole和3,3'，4,4'-tetrathia-1,1'-biphospholeπ共轭体系：S产生影响

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摘要

Conjugated systems based on phospholes and 1,1′-biphospholes bearing 3,4-ethylenedithia bridges have been prepared using the Fagan-Nugent route. The mechanism of this organo-metallic route leading to intermediate zirconacyclopentadienes has been investigated by using theoretical calculations. This study revealed that the oxidative coupling leading to zirconacyclo- pentadienes is favored over oxidative addition within the S-C ≡ C bond both thermodynamically and kinetically. The impact of the presence of the S atoms on the optical and electrochemical behavior of the phospholes and 1,1′-bi-phospholes has been systematically evaluated both experimentally and the oretically. A comparison with their "all-carbon" analogues is provided. Of particular interest, this comparative study revealed that the introduction of S atoms has an impact on the electronic properties of phosphole-based conjugated systems. A decrease of the HOMO-LUMO separation and a stabilization of the LUMO level were observed. These general trends are also observed with 1,1′-biphospholes exhibiting σ-π conjugation. The P atom of the 3,4-ethylenedithiaphospholes can be selectively oxidized by S _8 or O_2. These P modifications result in a lowering of the HOMO-LUMO separation as well as an increase of the reduction and oxidation potentials. The S atoms of the 3,4-ethylenedithia bridge of the 2,5-phosphole have been oxidized using m-chloroperoxybenzoic acid. The resulting 3,4-ethylenesulfoxide oxophosphole was characterized by an X-ray diffraction study. Experimental and theoretical studies show that this novel chemical manipulation results in an increase of the HOMO-LUMO separation and an important decrease of the LUMO level. The electropolymerization of 2-thienyl-capped 3,4-ethylenedi-thiathioxophosphole and 1,1′-biphos-phole is reported. The impact of the S substituents on the polymer properties is discussed.
机译：已使用Fagan-Nugent路线制备了基于带有3,4-乙二胺基桥的磷酸酯和1,1'-双磷的共轭体系。已通过理论计算研究了这种有机金属途径导致中间体氧化锆环戊二烯的机理。这项研究表明，在热力学和动力学上，导致氧化锆环戊二烯的氧化偶合优于S-C≡C键中的氧化加成。实验和理论上都已经系统地评估了S原子的存在对磷脂和1,1'-双磷脂的光学和电化学行为的影响。提供了与它们的“全碳”类似物的比较。特别令人感兴趣的是，该比较研究表明，S原子的引入对基于磷脂的共轭体系的电子性能产生影响。观察到HOMO-LUMO分离的减少和LUMO水平的稳定。这些一般趋势也可以通过具有σ-π共轭作用的1,1'-联磷酸酯观察到。 3,4-乙二硫磷的P原子可以被S _8或O_2选择性氧化。这些P修饰导致HOMO-LUMO分离的降低以及还原和氧化电位的增加。 2,5-膦基的3,4-乙二胺桥的S原子已使用间氯过氧苯甲酸氧化。通过X射线衍射研究表征了所得的3，4-亚乙氧基氧代磷腈。实验和理论研究表明，这种新颖的化学操作导致HOMO-LUMO分离的增加和LUMO含量的重要降低。报道了2-噻吩基封端的3，4-亚乙基二噻吩并氧和1，1′-联磷孔的电聚合。讨论了S取代基对聚合物性能的影响。

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