Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore

Subhadip Goswami, Russell W. Winkel, Erkki Alarousu, Ion Ghiviriga, Omar F. Mohammed, Kirk S. Schanze

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

A pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units. (Figure Presented).
Original languageEnglish (US)
Pages (from-to)11735-11743
Number of pages9
JournalThe Journal of Physical Chemistry A
Volume118
Issue number50
DOIs
StatePublished - Dec 5 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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