Intramolecular charge transfer with fluorazene and N-phenylpyrrole

Sergey I. Druzhinin, Sergey A. Kovalenko, Tamara A. Senyushkina, Attila Demeter, Klaas A. Zachariasse

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

The reaction from the initially prepared locally excited (LE) precursor to the intramolecular charge transfer (ICT) state of the planarized fluorazene (FPP) is investigated and compared with its flexible counterpart N-phenylpyrrole (PP). The fluorescence spectra of FPP and PP at 25 °C in solvents of different polarity reveal that the onset of a LE → ICT reaction occurs at lower polarity (tetrahydrofuran, ε = 7.39) for FPP than for PP (1,2-dichloroethane, ε = 10.4). In accordance with this observation, the ICT reaction enthalpy -△H is larger for FPP than for PP, 16.7 versus 6.7 kJ/mol in ethyl cyanide (EtCN). The larger ICT efficiency of FPP is related to the smaller energy gap between the two lowest excited singlet states △E(S1,S2): 3680 cm-1 for FPP and 4070 cm-1 for PP in n-hexane, as would be expected in the context of the PICT model. From picosecond fluorescence decays in EtCN at -45 °C it is found that the LE → ICT reaction rate constant ka of FPP is with 9.8 × 1010 s-1 considerably larger than that of PP with 3.9 × 1010 s-1. From femtosecond transient absorption spectra in acetonitrile (MeCN) at 22 °C, an ICT reaction time of 1.6 ps is obtained for FPP, shorter than the 4.0 ps determined for PP. The results show that a perpendicular twist of the pyrrole and phenyl subgroups is not required for an efficient ICT reaction with PP, the planarization of FPP even making this reaction faster. The similarity of the ESA spectra of FPP with those of PP in MeCN, with ICT absorption maxima at 365 nm (FPP) and 370 nm (PP), leads to the conclusion that both ICT states have a planar structure.

Original languageEnglish
Pages (from-to)1621-1632
Number of pages12
JournalJournal of Physical Chemistry A
Volume114
Issue number4
DOIs
Publication statusPublished - Mar 1 2010

    Fingerprint

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Druzhinin, S. I., Kovalenko, S. A., Senyushkina, T. A., Demeter, A., & Zachariasse, K. A. (2010). Intramolecular charge transfer with fluorazene and N-phenylpyrrole. Journal of Physical Chemistry A, 114(4), 1621-1632. https://doi.org/10.1021/jp909682p