Origin of the Red Sites and Energy Transfer Rates in Single MEH-PPV Chains at Low Temperature

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 orde…

Observation of Very Narrow Linewidths in the Fluorescence Excitation Spectra of Single Conjugated Polymer Chains at 1.2 K

Fluorescence emission and excitation spectra of single poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] polymer molecules embedded in poly(methylmethacrylate) have been recorded at 1.2 K. The ubiquitous spectral diffusion causes large variations in the spectral shape and apparent linewidth in the emission spectra. Nevertheless, we find very narrow (approximately 0.1 cm(-1)) purely electronic zero-phonon lines in the excitation spectra, which are 2 orders of magnitude smaller than previous estimates of the homogeneous linewidth. These results complement the molecular description of the low energy transitions in conjugated polymers.

Single Molecule Studies of a Ladder Type Conjugated Polymer: Vibronic Spectra, Line Widths, and Energy Transfer

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…

Superexchange-mediated electronic energy transfer in a model dyad

On the basis of time-dependent density functional theory (TD-DFT) calculations coupled to the polarizable continuum model (PCM) and single molecule spectroscopic studies, we provide a detailed investigation of excitation energy transfer within a model bi-chromophoric system where a perylene monoimide (PMI) donor is bridged to a terrylene diimide (TDI) acceptor through a ladder-type pentaphenylene (pPh) spacer. We find that the electronic excitation on the PMI donor significantly extends over the bridge giving rise to a partial charge transfer character and inducing a approximately 3-fold increase in the electronic interaction between the chromophores, which explains the failure of the Först…

Fluorescence excitation and emission spectroscopy on single MEH-PPV chains at low temperature.

Fluorescence emission and excitation spectra of single MEH-PPV polymer molecules dispersed in thin PMMA films have been recorded at 1.2 and 20 K. We observe single as well as multichromophore emission in single chain emission spectra, whereby the relative fractions depend on the two different molecular weights (50 and 350 kDa) studied. The molecular weight also affects the distribution of peak emission maxima, which is monomodal (bimodal) for the low (high) molecular weight. The appearance of an additional "red" subpopulation for the high molecular weight sample is attributed to interactions of multiple chromophores from a sufficiently flexible single chain. The comparison of emission spect…

Faltung einzelner konjugierter Polymerketten während des Annealing-Prozesses

The folding of individual conjugated polymer chains during annealing.

Single-Molecule Spectroscopy of MEH-PPV Polymer Molecules in Different Host Matrices

Fluorescence emission and excitation spectra of single MEH-PPV molecules dispersed in three different host polymers (PMMA, PS, and Zeonex) have been recorded at 1.2 K. We observed only minor effects of the host matrix on the following parameters: the ratios of single-chromophoric to multichromophoric emission, the widths of the distributions of emission maxima, and the (generally very low) fraction of emission spectra with sharp zero-phonon lines. The differences are tentatively attributed to different conformations of MEH-PPV chains, subtle variations in local chromophore−matrix interactions, and/or different distributions of conjugation lengths of emitting chromophores, respectively. Usin…