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Issue 29, 2006
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The photophysical properties of chromophores at high (100 mM and above) concentrations in polymers and as neat solids

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Abstract

The absorption, fluorescence, and photostability of five conjugated chromophores: perylene, 2,5,8,11-tetra-t-butyl perylene (TTBP), perylene orange (PO), perylene red (PR), and a zwitterionic Meisenheimer complex (MHC), are studied as a function of concentration in poly(methyl methacrylate) (PMMA). At 1 mM concentrations, all five molecules exhibit properties consistent with unaggregated chromophores. At higher concentrations, perylene and PO both exhibit excimer formation, while TTBP, PR, and the MHC retain their monomeric fluorescent lineshapes. In these three molecules, however, the fluorescence decay times decrease by 10% (TTBP) to 50% (MHC) at concentrations of 100 mM in PMMA. The fluorescence properties of these highly concentrated samples are sensitive to the sample preparation conditions. In the neat solid where the effective concentration is on the order of 1 M, all three molecules exhibit very fast fluorescence decays, on the order of 150 ps or less, despite the fact that they retain their basic monomeric fluorescence lineshape. In addition to the enhanced nonradiative decay at high concentrations, these three molecules also undergo a concentration-dependent photobleaching. The combined effects of intermolecular nonradiative decay channels and photobleaching appear to be a general obstacle to achieving highly concentrated dye-doped solids.

Graphical abstract: The photophysical properties of chromophores at high (100 mM and above) concentrations in polymers and as neat solids

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Publication details

The article was received on 26 Apr 2006, accepted on 31 May 2006 and first published on 19 Jun 2006


Article type: Paper
DOI: 10.1039/B605925B
Citation: Phys. Chem. Chem. Phys., 2006,8, 3453-3459
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    The photophysical properties of chromophores at high (100 mM and above) concentrations in polymers and as neat solids

    R. O. Al-Kaysi, T. Sang Ahn, A. M. Müller and C. J. Bardeen, Phys. Chem. Chem. Phys., 2006, 8, 3453
    DOI: 10.1039/B605925B

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