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Zeitschrift für Physikalische Chemie

International journal of research in physical chemistry and chemical physics

Ed. by Rademann, Klaus

12 Issues per year


IMPACT FACTOR 2016: 1.012

CiteScore 2016: 0.99

SCImago Journal Rank (SJR) 2016: 0.463
Source Normalized Impact per Paper (SNIP) 2016: 0.470

Online
ISSN
2196-7156
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Volume 227, Issue 6-7 (Jun 2013)

Issues

Double Hydrogen Transfer in Low Symmetry Porphycenes

Piotr Fita / Piotr Ciacka / Igor Czerski / Marek Pietraszkiewicz / Czeslaw Radzewicz / Jacek Waluk
Published Online: 2013-03-25 | DOI: https://doi.org/10.1524/zpch.2013.0372

Abstract

The rate constants of intramolecular double hydrogen transfer have been determined for of tert-butyl-substituted porphycenes: 2-tert-butyl-, 2,7-di-tert-butyl-, 2,7,12-tri-tert-butyl-, and 2,7,12,17-tetra-tert-butylporphycene using femtosecond pump-probe polarization spectroscopy. The rates increase monotonically with the number of substituents. As is the case for other porphycenes studied so far, the tautomerization becomes slower after excitation to the lowest excited singlet state. The potential for the trans-trans self-exchange reaction is symmetrical in di- and tetra-tert-butyl substituted derivatives, but not for the singly and triply substituted ones. Our studies enabled determination of the relative populations of nonequivalent tautomers and thus of the equilibrium constants in S0 and S1 states, as well as estimation of ground and excited state activation energies for the tautomerization process.

Keywords: Porphycenes; Tautomerism; Hydrogen Transfer; Pump-Probe Polarized Spectroscopy

About the article

* Correspondence address: Polish Academy of Sciences, Institute of Physical Chemistry, Kasprzaka 44/52, 01-224 Warsaw, Polen,


Published Online: 2013-03-25

Published in Print: 2013-06-01


Citation Information: Zeitschrift für Physikalische Chemie, ISSN (Online) 2196-7156, ISSN (Print) 0942-9352, DOI: https://doi.org/10.1524/zpch.2013.0372.

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