Understanding subtle aspects of photophysical behavior is the key to design and synthesize new and improved luminescent materials. We contribute to this with an in-depth photophysical characterization of the binuclear copper complex Cu(i)-NHetPHOS-tris-m-tolylphosphine (1), a member of a recently established emitter class for ultra-efficient, printed organic light-emitting diodes (OLEDs). To this end we studied 1 in solution and in solid form, i.e. neat film and KBr-pellet, by means of femtosecond time-resolved transient absorption/reflectivity, time-correlated single photon counting (TCSPC), and nanosecond time-resolved step-scan FTIR spectroscopy. Using these methods, we explore the photoinduced dynamics from ultrafast Franck-Condon state deactivation until the decay of the luminescent states. Upon photoexcitation, we observed multiexponential dynamics in both solution (e.g. acetonitrile 0.8 ps, 59 ps, 3 ns, 11-13 ns) and in solid state (e.g. neat film 0.3 ps, 35 ps, 670 ps, 0.5-1 μs, 3.5-4.5 μs) with four to five time-constants that significantly depend on the type of sample. Quantum chemical calculations at the DFT level in combination with step-scan vibrational spectroscopy provided structural information about the electronic ground state S and the lowest lying excited state T, and show that the latter is populated within 1 μs after photoexcitation. We found thermally activated delayed fluorescence (TADF) for this complex, which has been suggested to be the cause for its high efficiency in printed OLED devices. The results suggest that non-radiative processes, lowering the luminescence quantum yield in solution, are active on the ns to μs timescale.
Deactivation processes of photoexcited (λex = 580 nm) phycocyanobilin (PCB) in methanol were investigated by means of UV/Vis and mid-IR femtosecond (fs) transient absorption (TA) as well as static fluorescence spectroscopy, supported by density-functional-theory calculations of three relevant ground state conformers, PCBA, PCBB and PCBC, their relative electronic state energies and normal mode vibrational analysis. UV/Vis fs-TA reveals time constants of 2.0, 18 and 67 ps, describing decay of PCBB*, of PCBA* and thermal re-equilibration of PCBA, PCBB and PCBC, respectively, in line with the model by Dietzek et al. (Chem Phys Lett 515:163, 2011) and predecessors. Significant substantiation and extension of this model is achieved first via mid-IR fs-TA, i.e. identification of molecular structures and their dynamics, with time constants of 2.6, 21 and 40 ps, respectively. Second, transient IR continuum absorption (CA) is observed in the region above 1755 cm−1 (CA1) and between 1550 and 1450 cm−1 (CA2), indicative for the IR absorption of highly polarizable protons in hydrogen bonding networks (X–H…Y). This allows to characterize chromophore protonation/deprotonation processes, associated with the electronic and structural dynamics, on a molecular level. The PCB photocycle is suggested to be closed via a long living (> 1 ns), PCBC-like (i.e. deprotonated), fluorescent species.
Ultrafast electronic dynamics and UV absorption of phosphine–ligated (L) coinage metal complexes [Ag2(L)2]2, [AgAu(L)2]2+ and [Au2(L)2]2+ reveal the influence of intermetallic interaction on electronic states. Isomorphic exchange by AuI presumably accelerates ISC rate.
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