Dissecting Trichalcogenasumanenes: π-Bowl to Planar, Invertible Curvature, and Chiral Polycycles.
Dissecting Trichalcogenasumanenes: π-Bowl to Planar, Invertible Curvature, and Chiral Polycycles.
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DOI：
10.1002/chem.201703469
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发表时间：
2017-10
期刊：
影响因子：
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通讯作者：
Xueqing Hou;Xuexiang Li;Chun‐Lin Sun;Li-Chuan Chen;Yantao Sun;Zhe Liu;Hao‐Li Zhang;X. Shao
中科院分区：
文献类型：
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作者：
Xueqing Hou;Xuexiang Li;Chun‐Lin Sun;Li-Chuan Chen;Yantao Sun;Zhe Liu;Hao‐Li Zhang;X. Shao
巴基碗三硫化物在氧化时表现出侧翼苯环的裂解，这通过将各种脒部分融合到外围区域来导致它们的分解。通过逐渐将脒的环尺寸从五元增加到六元和七元，分子工程产生了[7-5-6]-、[7-6-6]-和[7-7-6]-稠合多环。三个系统在分子几何形状、堆积图案和光电特性方面各不相同。 [7-5-6]-稠合外壳采用扁平骨架，表现出强发射，荧光量子产率高达52.3%，并经历双光子吸收过程。 [7-6-6]稠合具有分子几何倒转的曲率，形成紧密堆叠的弯曲π体系，显示出延伸至700 nm的宽吸收，并表现出p型半导体行为，空穴迁移率为4.4×10-3 cm2 V-1 s-1 。 [7-7-6]稠合分子具有高度扭曲的骨架，表现出稳定的手性，并且在溶液和固态下均表现出红色发射。三硫代素马烯手术是一种有前途的方法来制造具有多种功能的多环化合物。
The buckybowl trichalcogenasumanenes show cleavage of flanking benzene ring upon oxidation, which leads their dissection by fusing various amidine moieties onto peripheral region. By gradually increasing the ring size of amidine from five- to six- and seven-membered, the molecule engineering results in the [7-5-6]-, [7-6-6]-, and [7-7-6]-fused polycycles. Three systems are distinct in the molecular geometries, packing motifs, and optoelectronic properties. The [7-5-6]-fused case adopts the flat backbone, displays strong emission with the fluorescence quantum yield up to 52.3 %, and undergoes a two-photon absorption process. The [7-6-6]-fused one is of a curvature with molecular geometry inversion, forms a tight stack of curved π-system, shows broad absorption extended to 700 nm, and exhibits the p-type semiconducting behavior with hole mobility of 4.4×10-3 cm2 V-1 s-1 . The [7-7-6]-fused one possesses the highly twisted skeleton to show stable chirality, and exhibits red emission in both solution and solid state. The surgery on trichalcogenasumanene is a promising approach to create polycycles with diverse functionalities.