Pressure Modulation of Backbone Conformation and Intermolecular Distance of Conjugated Polymers Toward Understanding the Dynamism of π‑Figuration of their Conjugated System

Continuous tuning of the backbone conformation and interchain distance of a π-conjugated polymer is an essential prerequisite to unveil the inherent electrical and optical features of organic electronics. To this end, applying pressure in a hydrostatic medium or diamond anvil cell is a facile approach without the need for side-chain synthetic engineering. We report the development of high-pressure, time-resolved microwave conductivity (HP-TRMC) and evaluation of transient photoconductivity in the regioregular poly­(3-hexylthiophene) (P3HT) film and its bulk heterojunction blend with methanofullerene (PCBM). X-ray diffraction experiments under high pressure were performed to detail the pressure dependence of π-stacking and interlamellar distances in P3HT crystallites and PCBM aggregates. The HP-TRMC results were further correlated with high-pressure Raman spectroscopy and density functional theory calculation. The increased HP-TRMC conductivity of P3HT under pressure was found to be relevant to the planarity of the backbone conformation and intramolecular hole mobility. The effects of pressure on the backbone planarity are estimated to be ∼0.3 kJ mol–1 based on the compressibility derived from the X-ray diffraction under high pressure, suggesting the high enough energy to cause modulation of the planarity in terms of the Landau-de Gennes free energy of isolated P3HT chains as 0.23 kJ mol–1. In contrast, the P3HT:PCBM blend showed a simple decrease in photoconductivity irrespective of the identical compressive behavior of P3HT. A mechanistic insight into the interplay of intra- and intermolecular mobilities is a key to tailoring the dynamic π-figuration associated with electrical properties, which may lead to the use of HP-TRMC for exploring divergent π-conjugated materials at the desired molecular arrangement and conformation.