The lithium κ¹-enamides, Me₂NSiMe₂CHC(Ph)-{2,6-(R¹)₂-4-(R²)C₆H₂}NLi·3THF (R¹ = ⁱPr, R² = H L1; R¹ = Et, R² = H L2; R¹ = Me, R² = H L3; R¹ = R² = Me L4; R¹ = Et, R² = Me L5), in the presence of titanium tetrachloride, undergo intermolecular rearrangement cyclization reactions resulting in 1,3-migration of the silicon groups and the elimination of dimethylamine affording five examples of bis-azasilicon-bridged heterocyclic arylamines, [{2,6-(R¹)₂-4-(R²)C₆H₂}N(Ph)CCSiMe₂]₂ (R¹ = ⁱPr, R² = H D1; R¹ = Et, R² = H D2; R¹ = Me, R² = H D3; R¹ = R² = Me D4; R¹ = Et, R² = Me D5) in good yield, respectively. The molecular structures of D1–D5 show the two fused N–Si–C–C–C rings to be co-planar indicative of extended π-conjugation, while their photophysical properties reveal them to be green/blue emitting with high luminescence quantum yields (Φ_F range: 75–99%). Furthermore, the compounds D serve as versatile reactants undergoing ring opening on hydrolysis to afford the saturated 1,4-diimines [{2,6-(R¹)₂-4-(R²)C₆H₂}N(Ph)C-CH₂]₂ (R¹ = ⁱPr, R² = H E1; R¹ = Et, R² = H E2; R¹ = Me, R² = H E3; R¹ = R² = Me E4; R¹ = Et, R² = Me E5). Alternatively, D can be employed in a redox-promoted cascade reaction to afford the conjugated 1,4-diimines, (E)-[{2,6-(R¹)₂-4-(R²)C₆H₂}NC(Ph)CH]₂ (R¹ = ⁱPr, R² = H F1; R¹ = Et, R² = H F2; R¹ = Me, R² = H F3; R¹ = R² = Me F4; R¹ = Et, R² = Me F5). In addition to D1–D5, E1–E3, E5, F2 and F3 have been the subject of single crystal X-ray diffraction studies.

中文翻译：

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氮杂硅桥连的杂环芳基胺：合成，结构和光物理性质†

锂κ ^1个-enamides中，Me ₂ NSiMe ₂ CHC（PH） - {2,6-（R ¹）₂ -4-（R ²）C ₆ H ^ ₂ } NLi等·3THF（R ¹ =^我镨，R ² = H L1 ; R ¹ = Et，R ² = H L2 ; R ¹ = Me，R ² = H L3 ; R ¹ = R ² = Me L4 ; R ¹ = Et，R ² = Me L5），在四氯化钛存在下，进行分子间重排环化反应，导致硅基团进行1,3迁移并消除二甲基胺，从而得到双氮杂硅桥连的杂环芳基胺的五个例子，[{2,6-（R ¹）₂ -4-（R ²）C ₆ H ₂ } N（Ph）CCSiMe ₂ ] ₂（R ¹ = ⁱ Pr，R ² = H D1 ; R ¹ = Et，R ² = H D2 ; R ¹ = Me，R ² = H D3； R ¹ = R² =我D4 ; R ¹＝ Et，R ²＝ Me D5）分别具有良好的产率。D1-D5的分子结构显示两个稠合的N-Si- CC-CC环是共面的，表示扩展了π共轭，而它们的光物理性质表明它们是绿色/蓝色发射的，具有高发光量子产率（ Φ _˚F范围：75-99％）。此外，化合物D用作通用反应物，其在水解时经历开环反应，得到饱和的1,4-二亚胺[{2,6-（R ¹） ₂ -4-（R ²）C ₆ H ₂ } N（Ph） C-CH ₂] ₂（R ¹ = ⁱ Pr，R ² = H E1； R ¹ = Et，R ² = H E2； R ¹ = Me，R ² = H E3； R ¹ = R ² = Me E4； R ¹ = Et ，R ² = Me E5）。或者，可以将D用于氧化还原促进的级联反应中，以得到共轭的1，4-二亚胺，（E）-[{2,6-（R ¹）₂ -4-（R ²）C ₆ H₂ } NC（Ph）CH] ₂（R ¹ = ⁱ Pr，R ² = H F1 ; R ¹ = Et，R ² = H F2 ; R ¹ = Me，R ² = H F3 ; R ¹ = R ²＝ Me F4； R ¹＝ Et，R ²＝ Me F5）。除D1-D5外， E1-E3， E5， F2和F3也是单晶X射线衍射研究的主题。