Emitters for organic light‐emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) require small singlet (S1)‐triplet (T1) energy gaps as well as fast intersystem crossing (ISC) transitions. These transitions can be mediated by vibronic mixing with higher excited states Sn and Tn (n=2, 3, 4, …). For a prototypical TADF emitter consisting of a triarylamine and a dicyanobenzene moiety (TAA‐DCN) it is shown that these higher states can be located energetically by time‐resolved near‐infrared (NIR) spectroscopy.
Linearly coordinated copper(I) carbene complexes, such as [1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene]‐(2‐picoline)copper(I) tetrafluoroborate (1), exhibit promising photophysical properties with regard to organic light emitting diode (OLED) applications. Their emission characteristics strongly depend on the surrounding (crystal, matrix, and solution). Here, the behavior of 1 in solution is scrutinized by steady state as well as femtosecond spectroscopy. In coordinating solvents, like acetonitrile and alcohols, 1 is shown to bind solvent molecules as ligands. In non‐coordinating solvents, femtosecond UV/Vis absorption spectroscopy reveals a tri‐exponential decay with time constants of 0.3 ps, 900 ps, and 0.7 μs. The time constants are assigned with the aid of quantum chemistry. A more complex decay is observed in coordinating solvents.
A previous quantum chemical study (M. Bracker et al., Phys. Chem. Chem. Phys. 2019, 21, 9912–9923) on the excited state properties of fluorinated derivatives of the flavin chromophore promised an increased fluorescence performance of the derivative 7,8‐difluoro‐10‐methyl‐isoalloxazine (7,8‐dF‐MIA). Here, we describe the synthesis of 7,8‐dF‐MIA, its ribityl derivative, and for reason of comparison 9‐F‐MIA. The compounds dissolved in water (H2O and D2O) were characterized by steady state, time resolved, and fluorescence correlation spectroscopy. The experiments confirm the increase of the fluorescence quantum yield of 7,8‐dF‐MIA (0.42 in H2O) compared to MIA (0.22) predicted by quantum chemistry. The anticipated reduction of the fluorescence quantum yield for 9‐F‐MIA is also confirmed experimentally. The quantum chemical computations as well as the spectroscopic observations attribute the increased fluorescence quantum yield of 7,8‐dF‐MIA predominantly to a decrease of the rate constant of intersystem crossing. Switching from H2O to D2O as a solvent is shown to increase fluorescence quantum yields (0.53 for 7,8‐dF‐MIA) and lifetimes of all fluorinated MIA derivatives. This can be attributed to a Förster type energy transfer from the excited chromophore to vibrational overtones of water and further water‐mediated deactivation processes.
The photophysics of 2-cyanoindole (2-CI) in solution (water, 2,2,2-trifluoroethanol, acetonitrile‚ and tetrahydrofuran) was investigated by steady-state as well as time resolved fluorescence and absorption spectroscopy. The fluorescence quantum yield of 2-cyanoindole is strongly sensitive to the solvent. In water the quantum yield is as low as 4.4 × 10–4. In tetrahydrofuran, it amounts to a yield of 0.057. For 2-CI dissolved in water, a bi-exponential fluorescence decay with time constants of ∼1 ps and ∼8 ps is observed. For short wavelength excitation (266 nm) the initial fluorescence anisotropy is close to zero. For excitation with 310 nm it amounts to 0.2. In water, femtosecond transient absorption reveals that the fluorescence decay is solely due to internal conversion to the ground state. In aprotic solvents, the fluorescence decay takes much longer (acetonitrile: ∼900 ps, tetrahydrofuran: ∼2.6 ns) and intersystem crossing contributes.
Graphical abstract
The Front Cover illustrates a full strike in fluorescence! Double fluorination of isoalloxazines at positions 7 and 8, to which quantum chemistry has pointed at, gives compounds with the highest fluorescence quantum yields reported so far for its class. The mallet shows the power of fluorination for the modulation of intersystem crossing when aimed delicately. The corresponding difluorinated flavins show even higher quantum yields when using deuterated solvents. Cover design by Marie Glasewald. More information can be found in the Research Article by Claus A. M. Seidel, Peter Gilch, Constantin Czekelius and co‐workers.
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