Metal coordination induced π-extension and triplet state production in diketopyrrolopyrrole chromophores.
Triplet state photophysics has been generated in two distinct diketopyrrolopyrrole (DPP) chromophores terminated with either phenyl (1) or thienyl (2) spacers, when sandwiched between two Ir(III) complexes using bipyridyl linkers. Upon coordination of the bpy-DPP-bpy subunit resulting in its planarization, the π-conjugation in the DPP chromophore formally extends and was manifested as a substantial red shift in the absorption and fluorescence profiles of 1 and 2. Low energy excitation of these dinuclear metal complexes produced strongly quenched singlet fluorescence, generated quite intense long-lived (τ ∼ 3 μs) absorption transients in the red, sensitized (1)O(2) photoluminescence centered at 1270 nm in aerated solutions, and yielded low temperature near-IR phosphorescence in 1 centered at 950 nm.
Department of Chemistry & Center for Photochemical Sciences, Bowling Green State University, Bowling Green, Ohio 43403, United States.
Catherine E
CE
McCusker
Delphine
D
Hablot
Raymond
R
Ziessel
Felix N
FN
Castellano