The near-infrared photochemistry of porphine imbedded in an N-hexane matrix |
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| Affiliation: | 1. Department of Chemistry, University of California, Berkeley, California 94720, and Materials and Chemical Sciences Division of the Lawrence Berkeley Laboratory, Berkeley, California 94720 USA;2. Institut für Physikalische Chemie, Universität Freiburg, Albertstr. 21, D-7800 Freiburg i. Br., West Germany;1. Department of Physics, Faculty of Science, Higher Education Center of Eghlid, Eghlid, 7381943885, Iran;2. Physics Department, College of Science, Shiraz University, Shiraz, 71946-84795, Iran;1. Institute of Cultural Heritage and History of Science & Technology, University of Science and Technology Beijing, 30 Xueyuan Road, China;2. Chinese Academy of Cultural Heritage, 2 Gaoyuan Street, Beijing, China;3. Zhejiang Province Museum, 25 Gushan Road, Hongzhou, China;4. Institute of Natural Sciences and Technology in Arts, Academy of Fine Arts in Vienna, Schiller Platz 3, A1010 Austria, |
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| Abstract: | The near-infrared induced tautomerization of free-base porphine incorporated in a n-hexane-d14 matrix is reported. Nernst glower irradiation on the NH stretch fundamental does not induce tautomerization, but irradiation in the regions 4000 < ν < 5100 cm−1 and 5630 < ν < 7700 cm−1 does induce tautomerization. Narrowband (8 cm−1 fwhm) laser irradiation studies in the NH symmetric plus antisymmetric stretch combination band region (6300 < ν < 6600 cm−1) show that the near-infrared induced tautomerization occurs at select wavelengths. Tautomer conversion in absence of site conversion is strong evidence that the observed photochemistry is due to porphine absorption and not hexane absorption. The estimated quantum yield of 3×10−5 for 6530 cm−1 irradiation is at least one order of magnitude larger than the quantum yield expected from RRKM theory. |
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