[Chem] Self-adjusted aromatic cation-π binding promotes controlled self-assembly of positively charged p-electronic molecules
作者：Zhelin Zhang, Bin Mu, Xiaohe Miao, Liang Wang, Huanjun Lu, Yue Ma, Wei Tian
关键字：self-assembly, charged π-electronic molecules, cation-π interactions, liquid crystals, Photocatalysis
论文来源：期刊
具体来源：Chem 2024, 10, 1279-1294
发表时间：2024年
Self-assembly of identically charged π-electronic molecules generates unique charged assemblies with properties not observed in corresponding electronically neutral analogs. However, electrostatic attraction between opposite charges typically leads to charge-by-charge assemblies that hinder the manifestation of desired functionalities. Herein, we present a self-adjusted aromatic cation-π binding strategy to address this challenge. The described approach involves a self-complementary design featuring double-site aromatic cation-π binding interactions that govern the self-assembly direction, resulting in positively charged columnar assemblies. The obtained columnar structures are controlled by the self-adjustment process inherent in the specific aromatic cation-π binding modes. We characterize the transition from alternate overlapping to helical stacking, which ultimately yields thermodynamically favorable columnar polymorphism, including molecular crystals and liquid crystals with tunable intra-/inter-columnar correlations. These charged columnar assemblies serve as efficient intrinsic CO2 reduction photocatalysts. The helically stacked columnar assemblies exhibit enhanced performance, thus highlighting the profound impact of molecular stacking modes on photocatalytic efficiency.
全文链接：https://doi.org/10.1016/j.chempr.2024.01.026