Homoconjugation in Light-Emitting Poly(phenylene methylene)s: Origin and Pressure-Enhanced PhotoluminescenceClick to copy article linkArticle link copied!
- Aleksandr Perevedentsev*Aleksandr Perevedentsev*Email: [email protected]Institute of Materials Science of Barcelona (ICMAB-CSIC), Campus of the UAB, 08193 Bellaterra, SpainMore by Aleksandr Perevedentsev
- Adrián Francisco-LópezAdrián Francisco-LópezInstitute of Materials Science of Barcelona (ICMAB-CSIC), Campus of the UAB, 08193 Bellaterra, SpainMore by Adrián Francisco-López
- Xingyuan ShiXingyuan ShiDepartment of Physics and Centre for Plastic Electronics, Imperial College London, SW7 2AZ London, U.K.More by Xingyuan Shi
- Andreas BraendleAndreas BraendleDepartment of Materials, ETH Zürich, Vladimir-Prelog-Weg 5, 8093 Zürich, SwitzerlandMore by Andreas Braendle
- Walter R. CaseriWalter R. CaseriDepartment of Materials, ETH Zürich, Vladimir-Prelog-Weg 5, 8093 Zürich, SwitzerlandMore by Walter R. Caseri
- Alejandro R. GoñiAlejandro R. GoñiInstitute of Materials Science of Barcelona (ICMAB-CSIC), Campus of the UAB, 08193 Bellaterra, SpainICREA, Passeig Lluís Companys 23, 08010 Barcelona, SpainMore by Alejandro R. Goñi
- Mariano Campoy-QuilesMariano Campoy-QuilesInstitute of Materials Science of Barcelona (ICMAB-CSIC), Campus of the UAB, 08193 Bellaterra, SpainMore by Mariano Campoy-Quiles
Abstract
The surprising optical properties of the non-π-conjugated polymer poly(phenylene methylene) (PPM) and its derivatives—that is, absorption in the 350–450 nm and photoluminescence (PL) in the 400–600 nm spectral regions—have been attributed to chromophores formed by homoconjugation along the polymer chain. The enabling role of homoconjugation, however, was hitherto ascertained primarily by excluding alternative origins of luminescence. The present study offers direct evidence for homoconjugation by employing optical and vibrational spectroscopy to investigate the interplay between the microstructure and solid-state optical properties of PPM and its derivative poly(2,4,6-trimethylphenylene methylene). In particular, polarized Raman and PL spectroscopy of melt-drawn fibers reveal a preferentially perpendicular orientation of the phenylene rings relative to the fiber axis and, simultaneously, a preferentially parallel orientation of the transition dipole moment. PL spectroscopy under applied hydrostatic pressure yields a nearly fourfold increase in PL intensity at 8 GPa, together with a surprising absence of excimer emission. These characteristics, being highly atypical of conventional π-conjugated polymers, highlight the different origin of the optical properties of PPMs and unique opportunities for applications.
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