Tunable SiN Hybrid Conjugated Materials

We report the synthesis of a family of N-aryl cyclosilazanes. The reaction of 1,2-bis­(trifluoro­methanesulfonate)­tetramethyl­disilane with para-substituted anilines gives six-membered rings with no observed condensation polymerization. X-ray crystallography reveals the cyclosilazane adopts a twist boat conformation with both nitrogens in a trigonal planar geometry. Solution phase UV–vis spectroscopic studies coupled with density functional theory calculations interrogate the ability of the nitrogen atom to bridge the σ- and π-conjugated moieties. Depending on the aromatic substituent, the cyclosilazane rings may be either more or less electron rich than an all silicon ring.本研究报道了一类N-芳基环硅氮烷（N-aryl cyclosilazanes）的合成方法。1,2-双(三氟甲磺酰氧基)四甲基二硅烷与对位取代苯胺发生反应，可生成六元环产物，未观察到缩聚反应发生。X射线晶体学（X-ray crystallography）分析显示，该环硅氮烷分子采取扭船式构象，且两个氮原子均呈现平面三角形配位几何构型。通过溶液相紫外-可见（UV–vis）光谱研究结合密度泛函理论（density functional theory）计算，本工作探究了氮原子桥连σ与π共轭片段的能力。根据芳香取代基的不同，该环硅氮烷环的电子丰富程度可高于或低于全硅环。