Supramolecular Assembly of Conjugated Polymers under Vibrational Strong Coupling.

ABSTRACT

Strong coupling plays a significant role in influencing chemical reactions and tuning material properties by modifying the energy landscapes of the systems. Here we study the effect of vibrational strong coupling (VSC) on supramolecular organization. For this purpose, a rigid-rod conjugated polymer known to form gels was strongly coupled together with its solvent in a microfluidic IR Fabry-Perot cavity. Absorption and fluorescence studies indicate a large modification of the self-assembly under such cooperative VSC. Electron microscopy confirms that in this case, the supramolecular morphology is totally different from that observed in the absence of strong coupling. In addition, the self-assembly kinetics are altered and depend on the solvent vibration under VSC. The results are compared to kinetic isotope effects on the self-assembly to help clarify the role of different parameters under strong coupling. These findings indicate that VSC is a valuable new tool for controlling supramolecular assemblies with broad implications for the molecular and material sciences.