Influence of the Conjugation Length on the Optical Spectra of Single Ladder-Type (p‑Phenylene) Dimers and Polymers

We employ low-temperature single-molecule photoluminescence spectroscopy on a π-conjugated ladder-type (p-phenylene) dimer and the corresponding polymer methyl-substituted ladder-type poly­(p-phenylene), MeLPPP, to study the impact of the conjugation length (π-electron delocalization) on their optical properties on a molecular scale. Our data show that the linear electron–phonon coupling to intramolecular vibrational modes is very sensitive to the conjugation length, a well-known behavior of organic (macro-) molecules. In particular, the photoluminescence spectra of single dimers feature a rather strong low-energy (150 cm^–1) skeletal mode of the backbone, which does not appear in the spectra of individual chromophores on single MeLPPP chains. We attribute this finding to a strongly reduced electron–phonon coupling strength and/or vibrational energy of this mode for MeLPPP with its more delocalized π-electron system as compared to the dimer. In contrast, the line widths of the purely electronic zero-phonon lines (ZPL) in single-molecule spectra do not show differences between the dimer and MeLPPP; for both systems the ZPLs are apparently broadened by fast unresolved spectral diffusion. Finally, we demonstrate that the low-temperature ensemble photoluminescence spectrum of the dimer cannot be reproduced by the distribution of spectral positions of the ZPLs. The dimer’s bulk spectrum is rather apparently broadened by electron–phonon coupling to the low-energy skeletal mode, whereas for MeLPPP the inhomogeneous bulk line shape resembles the distribution of spectral positions of the ZPLs of single chromophores.