Evidence for two forms, double hydrogen tunneling, and proximity of excited states in bridge-substituted porphycenes: supersonic jet studies.
Laser-induced fluorescence and dispersed fluorescence spectra measured in supersonic jets for 9,10,19,20-tetra-n-methylporphycene and 9,10,19,20-tetra-n-propylporphycene reveal, for both compounds, the presence of two different species which are assigned to trans and cis tautomeric forms. Doublet splitting of lines is observed, disappearing upon deuteration of the inner nitrogen atoms. This finding is interpreted as an indication of double hydrogen tunneling. The values of tunneling splitting are obtained for both ground and lowest singlet excited states. The splitting is similar for cis and trans forms, and the barrier for tautomerization is larger in the excited state. Due to the coupling of hydrogen motion with rotation of alkyl substituents, tautomerization occurs in an asymmetric double minimum potential, with the ordering of energy minima reversed upon excitation. The second singlet excited state is found to lie very close to S(1), thus facilitating an efficient radiationless depopulation.
Photochemistry and Spectroscopy Department and Laser Centre, Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland.
Alexander
A
Vdovin
Jerzy
J
Sepioł
Natalia
N
Urbańska
Marek
M
Pietraszkiewicz
Andrzej
A
Mordziński
Jacek
J
Waluk