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首页> 外文期刊>Chemistry: A European journal >N-Arylated 3,5-Dihydro-4H-dinaphtho[2,1-c:1’,2’-e]azepines: Axially Chiral Donors with High Helical Twisting Powers for Nonplanar Push–Pull Chromophores
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N-Arylated 3,5-Dihydro-4H-dinaphtho[2,1-c:1’,2’-e]azepines: Axially Chiral Donors with High Helical Twisting Powers for Nonplanar Push–Pull Chromophores

机译：N-化3,5-二氢-4H-二萘并[2,1-c：1′，2′-e] a庚子：具有高螺旋扭转力的轴向手性供体，用于非平面推挽发色团

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摘要

Axially chiral, N-arylated 3,5-dihydro-4H-dinaphtho[2,1-c:1’,2'-e]azepines have been prepared by short synthetic protocols from enantiopure 1,1’-bi(2,2’-naphthol) (BINOL) and anilines. Alkynes substituted with two N-phenyldinaphthazepine donors readily undergo a formal [2+2] cycloaddition, followed by retro-electrocyclization,with tetracyanoethene (TCNE) to yield donor-substituted 1,1,4,4-etracyanobuta- 1,3-dienes (TCBDs) featuring intense intramolecular chargetransfer (CT) interactions. A dicyanovinyl derivative substituted with one Nphenyldinaphthazepine donor was obtained by a “one-pot” oxidation/Knoevenagel condensation from the corresponding propargylic alcohol. Comparative electrochemical, X-ray crystallographic, and UV/Vis studies show that the electron-donor qualities of N- henyldinaphthazepine are similar to those of N,N-dimethylanilino residues. The circular dichroism (CD) spectrum of a push–pull chromophore incorporating the chiral donor moiety features Cotton effects of exceptional intensity. With their elongated shape and the rigidity of the chiral N-aryldinaphthazepine donors, these chromophores are effective inducers of twist distortion in nematic liquid crystals (LCs). Thus, a series of the dinaphthazepine derivatives was used as dopants in the nematic LC E7 (Merck) and high helical twisting powers (b) of the order of hundreds of mm~(-1) were measured. Theoretical calculations were employed to elucidate the relation between the structure of the dopants and their helical twisting power. For the derivatives with two dinaphthazepine moieties, a strong dependence of the b-values onthe structure and conformation of the linker between them was found.
机译：轴向手性，N-芳基化的3,5-二氢-4H-二萘并[2,1-c：1'，2'-e]氮杂have是通过对映纯的1,1'-bi（2,2）的短合成方法制备的'-萘酚）（BINOL）和苯胺。被两个N-苯基二萘并ze庚因供体取代的炔烃容易进行正式的[2 + 2]环加成，然后与四氰基乙烯（TCNE）进行逆电环化，生成供体取代的1,1,4,4-etracyanobuta-1,3-dienes （TCBD）具有强烈的分子内电荷转移（CT）相互作用。通过“一锅”氧化/ Knoevenagel缩合反应，从相应的炔丙醇中获得了一个N苯基二萘并氮杂供体取代的二氰基乙烯基衍生物。比较的电化学，X射线晶体学和UV / Vis研究表明，N-二氢萘并二氮杂ze庚因的电子给体质量与N，N-二甲基苯胺基残基相似。包含手性供体部分的推挽生色团的圆二色性（CD）光谱具有异常强度的棉花效应。这些生色团具有细长的形状和手性N-芳基二氮杂萘类供体的刚性，是向列型液晶（LC）扭曲扭曲的有效诱因。因此，在向列LC E7（Merck）中，使用了一系列的二萘并derivatives庚因衍生物作为掺杂剂，并测量了数百毫米〜（-1）的高螺旋扭曲力（b）。采用理论计算来阐明掺杂剂的结构与其螺旋扭转能力之间的关系。对于具有两个二萘并氮杂mo部分的衍生物，发现b值对它们之间的结构和构象的强烈依赖性。

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