1. Synthesis and Near-infrared Luminescence of a Deuterated Conjugated Porphyrin Dimer for Probing the Mechanism of Non-radiative Deactivation
- Author
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Paul A. Fleitz, Nicola Armaroli, Gianluca Accorsi, Harry L. Anderson, Joy E. Rogers, Michael J. Frampton, and Kenneth McEwan
- Subjects
Magnetic Resonance Spectroscopy ,Porphyrins ,Luminescence ,Metalloporphyrins ,Dimer ,Quantum yield ,Conjugated system ,Photochemistry ,Sensitivity and Specificity ,Biochemistry ,chemistry.chemical_compound ,polycyclic compounds ,Molecule ,Physical and Theoretical Chemistry ,Spectroscopy ,Spectroscopy, Near-Infrared ,Molecular Structure ,Organic Chemistry ,Stereoisomerism ,Reference Standards ,Porphyrin ,Fluorescence ,Zinc ,chemistry ,Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization ,Spectrophotometry, Ultraviolet ,Porphyrin dimer ,Dimerization - Abstract
beta,meso,beta-Fused porphyrin oligomers have many attractive photophysical features such as strong absorption in the near-IR at wavelengths greater than 1000 nm, and high two-photon cross sections. However their ultrafast S(1)-S(0) deactivation (k(d) > 10(11) s(-1)) limits potential applications. We have synthesised a deuterated fused porphyrin dimer to test whether deuteration influences the rate of non-radiative deactivation. An efficient synthetic strategy was developed, starting with deuteration of dipyrromethane. Deuteration of the zinc porphyrin dimer does not affect its fluorescence quantum yield in CD(2)Cl(2)(Phi(fD)/Phi(fH)= 1.00 +/- 0.05). This implies that the ultrafast non-radiative deactivation is not simply a consequence of the small S(1)-S(0) energy gap. Comparison with other conjugated porphyrin oligomers confirms that the deactivation rate in the edge-fused oligomers is faster than would be expected from the energy gap law. This result indicates that it should be possible to create near-IR dyes with similar S(1)-S(0) energy gaps to the beta,meso,beta-fused porphyrin oligomers but with slower rates of S(1)-S(0) decay.
- Published
- 2007
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