Second Order Phase Transition and Stabilizing CH???H and CH???S Interactions in Naphthyl End-Capped Bithiophene at 3.5 GPa

The semiconducting bithiophene systems are largely unexplored structurally at high-pressures. Here, we characterize the high-pressure structure and phase behavior of 5,5 '-bis(naphth-2-yl)-2,2 '-bithiophene (NaT2) by single crystal X-ray diffraction, photoluminescence and Raman compression measurements in the diamond anvil cell to 7.6 GPa. Experimental results are supported by empirical interaction energy calculations. NaT2 maintains its ambient pressure structure (P21/c) on compression but undergoes a subtle second-order phase transition at ca. 3.5 GPa. The newly formed phase at 4.0 GPa is characterized by the formation of a new S center dot center dot center dot H interaction between thiophene moieties in adjacent molecules, as well as by the emergence of a more favorable compression pathway in its long-chain direction. NaT2 also undergoes a band gap closure manifested as a distinct yellow to red color change on compression that is fully reversible on decompression.