Self-Assembling Behavior and Chiroptical Properties of Carbazole-Cored Phenyl Isoxazolyl Benzenes

• Published in: Journal of organic chemistry 2021-04, Vol.86 (8), p.5499-5505
• Main Authors: Ono, Yudai, Hirao, Takehiro, Ikeda, Toshiaki, Haino, Takeharu
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.0c03005

Carbazole-cored phenyl isoxazolyl benzenes possessing chiral moieties were synthesized. The molecules self-assembled to form stacked supramolecular assemblies in an isodesmic fashion in chloroform, whereas the molecules preferably assembled in a cooperative fashion in methylcyclohexane (MCH), which was determined by spectroscopic methods, including UV–vis absorption, fluorescence, and 1H NMR spectroscopy. Clear nucleation and elongation processes were observed in the plot of the degree of aggregation (αagg) against temperature, which allowed us to determine the elongation temperature (T e), the enthalpic gain in the elongation process (ΔH e), the equilibrium constant between nucleation and elongation (K a), and the degree of polymerization at the elongation temperature ([N n(T e)]). Circular dichroism (CD) and circularly polarized luminescence (CPL) studies revealed the formation of helically stacked assemblies in solution. Moreover, the majority-rule effect was clearly observed in the solutions of mixtures of (S)- and (R)-1, indicating the chiral amplification behavior of the helically stacked assemblies consisting of (S)- and (R)-1. AFM provided morphological insight into the assemblies on mica, which clearly indicates the formation of polymeric assemblies in the solid state.