Harada Kentaro, Sekiya Ryo, Haino Takeharu
Department of Chemistry, Graduate School of Advanced Science and Engineering, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan.
Angew Chem Int Ed Engl. 2022 Sep 26;61(39):e202209340. doi: 10.1002/anie.202209340. Epub 2022 Aug 18.
By utilizing a confined space inside a coordination capsule consisting of achiral components, we achieve trimeric structures composed of acetic acid and 2,3-disubstituted tartaric acid derivatives. Steric and electronic interactions between the substituents on the tartaric acid and 2,2'-bipyridyl arms of the capsule permit the transfer of the chirality of the tartaric acid to the capsule, resulting in diastereoenrichment of the host-guest complexes of up to 92 % de. The chiral templates can be washed away with diethyl ether, leaving an enantiomerically enriched capsule. The resulting capsule biases the dynamic axial chirality of a 4,4'-diacetoxybiphenyl guest carrying benzothiadiazole units, demonstrating guest-to-capsule and capsule-to-guest chirality transfer. The induced chirality on the bound guest enables it to emit circularly polarized luminescence in the NIR region, demonstrating the application of induced chirality for confined spaces for the generation of chiroptical properties.
通过利用由非手性成分组成的配位胶囊内部的受限空间，我们实现了由乙酸和2,3-二取代酒石酸衍生物组成的三聚体结构。酒石酸上的取代基与胶囊的2,2'-联吡啶臂之间的空间和电子相互作用使得酒石酸的手性能够转移到胶囊上，从而导致主客体配合物的非对映体富集度高达92%。手性模板可用乙醚洗去，留下对映体富集的胶囊。所得胶囊使带有苯并噻二唑单元的4,4'-二乙酰氧基联苯客体的动态轴向手性产生偏向，展示了客体到手性胶囊以及手性胶囊到客体的手性转移。结合客体上诱导产生的手性使其能够在近红外区域发射圆偏振光，证明了诱导手性在受限空间中用于产生手性光学性质的应用。
