Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore
Winkel, Russell W.
Mohammed, Omar F.
Schanze, Kirk S.
KAUST DepartmentKAUST Solar Center (KSC)
Physical Sciences and Engineering (PSE) Division
Chemical Science Program
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AbstractA 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).
SponsorsThis 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.
PublisherAmerican Chemical Society (ACS)