Effect of Substituent Position in Coumarin Derivatives on the Interfacial Assembly: Reversible Photodimerization and Supramolecular Chirality

Abstract

The Langmuir and Langmuir-Schaefer (LS) films of two coumarin derivatives, 4-octadecyloxylcoumarin (4-CUMC18) and 7-octadecyloxylcoumarin (7-CUMC18), were newly synthesized, and their interfacial assemblies were investigated. Owing to the different substituent position of the long octadecyloxy chain in the coumarin parent, the two compounds showed completely different behaviors in the interfacial assemblies. When they were spread at the air/water interface, 7-CUMC18 formed a monolayer while 4-CUMC18 formed a multilayer film on the water surface. The spreading films on the water surface were transferred onto solid substrates by a Langmuir-Schaefer method, and the transferred films were characterized by UV-vis, Fourier transfer infrared, X-ray diffraction, circular dichroism, and atomic force microscopy spectra. Different packing of the molecules in the multilayer films was observed. While coumarin groups stacked in a face-to-face way in 7-CUMC18 film, they stacked in a head-to-tail manner in 4-CUMC18 film. Furthermore, distinct properties of the multilayer films were observed. It is revealed that a reversible [2+2] photodimerization and photocleavage could be induced in the LS film of 7-CUMC18 under photoirradiation with UV light of 365 and 254 nm, respectively. No photodimerization occurred in the 4-CUMC18 film. However, the film of 4-CUMC18 showed a supramolecular chirality although the compound itself is achiral.