Boron-Doped Polycyclic π-Electron Systems with an Antiaromatic Borole Substructure That Forms Photoresponsive B–P Lewis Adducts,Journal of the American Chemical Society

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Boron-Doped Polycyclic π-Electron Systems with an Antiaromatic Borole Substructure That Forms Photoresponsive B–P Lewis Adducts
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-06-10 , DOI: 10.1021/jacs.1c04251
Naoki Ando ₁ , Takuya Yamada ₁ , Hiroki Narita ₁ , Niels N Oehlmann ₂ , Matthias Wagner ₂ , Shigehiro Yamaguchi _{1,

3}

Affiliation

Heteroatom doping is a powerful strategy to alter the electronic structure of polycyclic aromatic hydrocarbons (PAHs). Especially boron doping endows PAH scaffolds with electron-accepting character and Lewis acidic centers. Herein, we report that embedding a five-membered borole ring into a polycyclic skeleton imparts the π-system with antiaromatic character and thereby induces unique properties and behavior. A series of borole-embedded π-conjugated compounds were synthesized from teraryl precursors via a borylation/intramolecular electrophilic C–H borylation sequence. The obtained compounds exhibit planar structures with distorted geometries around the boron center and form columnar slipped face-to-face π-stacked structures. Among these compounds, a pyrene-fused derivative shows an intense emission with a high quantum yield in solution. This compound also exhibits high Lewis acidity, which reflects the antiaromatic character and strained structure of the borole substructure. This compound forms a Lewis acid–base adduct even with weakly Lewis basic phosphorus-containing polycyclic π-systems. Analyzing the crystal structure of the thus-obtained adduct revealed a complex between the boron- and phosphorus-embedded π-systems with a direct B–P dative bond. This complex undergoes photodissociation in the excited state and exhibits an emission exclusively from the base-free borole-embedded π-system.

中文翻译：

硼掺杂多环 π 电子系统具有形成光响应性 B-P 路易斯加合物的抗芳香硼烷亚结构

杂原子掺杂是改变多环芳烃 (PAH) 电子结构的有力策略。特别是硼掺杂赋予 PAH 支架以电子接受特性和路易斯酸性中心。在此，我们报告将五元硼环嵌入多环骨架赋予 π 系统以抗芳香特性，从而诱导独特的性质和行为。通过硼酸化/分子内亲电 C-H 硼酸化序列，从四芳基前体合成了一系列硼嵌入的 π 共轭化合物。获得的化合物表现出平面结构，在硼中心周围具有扭曲的几何形状，并形成柱状滑动面对面的 π 堆叠结构。在这些化合物中，芘稠合衍生物在溶液中显示出具有高量子产率的强烈发射。该化合物还表现出高路易斯酸度，这反映了硼酸亚结构的抗芳香特性和应变结构。该化合物即使与弱路易斯碱性含磷多环 π 系统也能形成路易斯酸碱加合物。分析由此获得的加合物的晶体结构揭示了硼和磷嵌入的 π 系统之间的复合物，具有直接的 B-P 配键。该复合物在激发态发生光解作用，并仅从嵌入无碱硼的 π 系统中发射出来。分析由此获得的加合物的晶体结构揭示了硼和磷嵌入的 π 系统之间的复合物，具有直接的 B-P 配键。该复合物在激发态经历光解，并仅从嵌入无碱硼的 π 系统中发射。分析由此获得的加合物的晶体结构揭示了硼和磷嵌入的 π 系统之间的复合物，具有直接的 B-P 配键。该复合物在激发态经历光解，并仅从嵌入无碱硼的 π 系统中发射。

更新日期：2021-07-07

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