Single poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) molecules dispersed in thin poly(methylmethacrylate) films have been investigated by fluorescence emission, excitation and time-resolved spectroscopy at 1.2 K. For the molecular weight studied (∼200 kDa) a bimodal distribution of emission maxima is observed. Based on a comparison of the spectroscopic properties of blue and red sites and on polarisation-resolved measurements, we argue in agreement with recent quantum-chemical calculations that the red subpopulation most probably does not arise from interchromophoric excitation delocalisation but is to be attributed to longer chromophoric units originating from ordered regions of a polymer chain, where due to constraints on the chain conformation larger conjugation lengths can be realised. In excitation spectra within the red spectral region we can identify multiple chromophoric units, among them chromophores without correspondence in the emission spectrum-donors of the intramolecular energy transfer. Zero-phonon lines of donor chromophores proved to be significantly broadened, indicating fast excited-state population decay due to energy transfer. Thus, a distribution of energy transfer times within MEH-PPV chains could be determined from donor zero-phonon line widths, with an average value of 3.9 ps. Our study represents the first direct measurement of energy transfer times in conjugated polymers, parameters that are crucial for the performance of many technical applications based on this class of material.

Confocal fluorescence microscopy and spectroscopy are employed to investigate single poly(ladder-type pentaphenylene) (LPPentP) molecules dispersed in thin poly(methyl methacrylate) (PMMA) films at 1.2 K. Emission spectra of single chains show single as well as multi-chromophore emission indicating variegated communication along the chains. The vibronic structure in the emission spectra resembles the one found for other ladder-type polymers. Purely electronic zero-phonon lines in emission are substantially broadened, most probably due to fast spectral diffusion. By surmounting the limitations of emission spectroscopy, nonemitting donor chromophores, which transfer their excitation energy in a radiationless manner to emitting chromophores, are accessed by excitation spectroscopy. Remarkably, by comparing the data of emitting and nonemitting chromophores a contribution to the zero-phonon excitation line width has to be considered which places a lower limit on the estimated energy transfer time of several picoseconds between adjacent chromophores. Finally, the data indicate qualitatively a restricted flexibility of LPPentP compared to poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV).