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

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    Type
    Article
    Authors
    Goswami, Subhadip
    Winkel, Russell W.
    Alarousu, Erkki
    Ghiviriga, Ion
    Mohammed, Omar F. cc
    Schanze, Kirk S.
    KAUST Department
    Chemical Science Program
    KAUST Solar Center (KSC)
    Physical Science and Engineering (PSE) Division
    Ultrafast Laser Spectroscopy and Four-dimensional Electron Imaging Research Group
    Date
    2014-12-05
    Online Publication Date
    2014-12-05
    Print Publication Date
    2014-12-18
    Permanent link to this record
    http://hdl.handle.net/10754/563925
    
    Metadata
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    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).
    Citation
    Goswami, S., Winkel, R. W., Alarousu, E., Ghiviriga, I., Mohammed, O. F., & Schanze, K. S. (2014). Photophysics of Organometallic Platinum(II) Derivatives of the Diketopyrrolopyrrole Chromophore. The Journal of Physical Chemistry A, 118(50), 11735–11743. doi:10.1021/jp509987p
    Sponsors
    This work was supported by the National Science Foundation (Grant No. CHE-1151624). The ultrafast spectroscopy was carried out with support from the King Abdullah University of Science and Technology.
    Publisher
    American Chemical Society (ACS)
    Journal
    The Journal of Physical Chemistry A
    DOI
    10.1021/jp509987p
    ae974a485f413a2113503eed53cd6c53
    10.1021/jp509987p
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Solar Center (KSC)

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