Investigation of the linear and nonlinear optical response of edge-linked conjugated zinc porphyrin oligomers by optical spectroscopy and configuration interaction techniques

D. Beljonne*, G. E. O'Keefe, P. J. Hamer, R. H. Friend, H. L. Anderson, Jean-Luc Bredas

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

100 Scopus citations

Abstract

We present a joint experimental and theoretical investigation of the linear and nonlinear optical response of butadiyne-linked zinc porphyrin oligomers. Efficient overlap between the chromophores leads to a large red-shift of the Q absorption band together with a splitting of the B band into two components when increasing the chain length from one to two repeating porphyrin units. Ultrafast pumb-probe measurements performed on these compounds show several well-defined features, associated with singlet excited state absorption. We also find clear evidence for the formation of longer-lived triplet excitons, resulting from very efficient singlet-triplet intersystem crossing processes. For the monomers, the assignment of the observed linear and photoinduced absorption features is supported by a Configuration Interaction description of the singlet and triplet excited states. In the case of the porphyrin dimer, agreement with the experimental results can only be obtained by considering a sizable cumulenic contribution in the excited-state geometry used as input for the CI calculations. The potential of porphyrin systems for Reverse Saturable Absorption and Nonlinear Optics is emphasized.

Original languageEnglish (US)
Pages (from-to)9439-9460
Number of pages22
JournalJournal of Chemical Physics
Volume106
Issue number23
DOIs
StatePublished - Jun 15 1997

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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