Murray, Ciaran and Dozova, Nadia and McCaffrey, John G. and Shafizadeh, Niloufar and Chin, Wuthurath and Broquier, Michel and Crepin, Claudine (2011) Visible luminescence spectroscopy of free-base and zinc phthalocyanines isolated in cryogenic matrices. Physical Chemistry Chemical Physics, 13. pp. 17543-17554. ISSN 1463-9076

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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.

Item Type:	Article
Keywords:	Visible luminescence spectroscopy; free-base and zinc phthalocyanines; cryogenic matrices;
Academic Unit:	Faculty of Science and Engineering > Chemistry
Item ID:	7839
Identification Number:	https://doi.org/10.1039/C1CP22039J
Depositing User:	Dr. John McCaffrey
Date Deposited:	01 Feb 2017 17:40
Journal or Publication Title:	Physical Chemistry Chemical Physics
Publisher:	Royal Society of Chemistry
Refereed:	Yes
URI:	http://pubs.rsc.org
Use Licence:	This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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