Helicity Manipulation of a Double-Paddled Binaphthyl in a Two-Dimensional Matrix Field at the Air–Water Interface
Masaki Ishii, Taizo Mori, Waka Nakanishi, Jonathan P. Hill, Hideki Sakai, Katsuhiko Ariga
Abstract
Molecular behavior and functionality are affected by their prevailing immediate environment. Molecular machines function according to conformational variations and have been studied largely in solution states. In order to access more highly complex functional molecular machines, it is necessary to analyze and control them in various environments. We have designed and synthesized a bisbinaphthyldurene (BBD) molecule that has two binaphthyl groups connected through a central durene moiety, allowing for the formation of several conformers. In density functional theory (DFT) calculations, BBD has five major conformers, denoted anti-1/anti-2/syn-1/syn-2/flat. It has been demonstrated that BBD exhibits different conformations in solution (anti-1 and syn-1) than on a gold surface (syn dimer and flat). In this work, the ratio of BBD conformations has been controlled in mixed monolayers with several different lipids at an air–water interface in order to compare conformational activity under different conditions. The conformations of BBD in transferred films obtained by using Langmuir–Blodgett techniques were estimated from circular dichroism spectra and DFT calculations. It has been found that the conformation of BBD in the mixed monolayer depends on its aggregated state, which has been controlled here by the mechanical properties and miscibility. In mixed monolayers with “hard” lipids having less miscibility with BBD as well as in cast film, BBD is self-aggregated and mostly forms stable anti-1 and syn-1 conformations, while unstable anti-2 and syn-2 conformers dominated in the more dispersed states involving “soft” lipids, which show good miscibility with BBD. Conformational changes in BBD are due to the formation of different aggregated states in each mixed monolayer according to the miscibility. Overall, BBD molecular conformations (and the resulting spectra) could be tuned by controlling the environment whether in solution, on a solid substrate, or in an admixture with lipids at the air–water interface.