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Issue 39, 2011
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Visible luminescence spectroscopy of free-base and zinc phthalocyanines isolated in cryogenic matrices

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Abstract

The absorption, emission and excitation spectra of ZnPc and H2Pc trapped in Ne, N2, Ar, Kr and Xe matrices have been recorded in the region of the Q states. A comparison of the matrix fluorescence spectra with Raman spectra recorded in KBr pellets reveals very strong similarities. This is entirely consistent with the selection rules and points to the occurrence of only fundamental vibrational transitions in the emission spectra. Based on this behaviour, the vibronic modes in emission have been assigned using results obtained recently on the ground state with large basis-set DFT calculations [Murray et al. PCCP, 12, 10406 (2010)]. Furthermore, the very strong mirror symmetry between excitation and emission has allowed these assignments to be extended to the excitation (absorption) bands. While this approach works well for ZnPc, coupling between the band origin of the S2(QY) state and vibrationally excited levels of S1(QX), limits the range of its application in H2Pc. The QX/QY state coupling is analysed from data obtained from site-selective excitation spectra, revealing pronounced matrix and site effects. From this analysis, the splitting of the QX and QY states has been determined more accurately than in any previous attempts.

Graphical abstract: Visible luminescence spectroscopy of free-base and zinc phthalocyanines isolated in cryogenic matrices

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Article information


Submitted
22 Jun 2011
Accepted
11 Aug 2011
First published
01 Sep 2011

Phys. Chem. Chem. Phys., 2011,13, 17543-17554
Article type
Paper

Visible luminescence spectroscopy of free-base and zinc phthalocyanines isolated in cryogenic matrices

C. Murray, N. Dozova, J. G. McCaffrey, N. Shafizadeh, W. Chin, M. Broquier and C. Crépin, Phys. Chem. Chem. Phys., 2011, 13, 17543
DOI: 10.1039/C1CP22039J

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