Heptazine derivatives are promising dopants for electroluminescent devices. Recent studies raised the question whether heptazines exhibit a small regular or an inverted singlet–triplet (IST) gap. It was argued that the S1 ← T1 reverse intersystem crossing (RISC) is a downhill process in IST emitters and therefore does not require thermal activation, thus enabling efficient harvesting of triplet excitons. Rate constants were not determined in these studies. Modeling the excited-state properties of heptazine proves challenging because fluorescence and intersystem crossing (ISC) are symmetry-forbidden in first order. In this work, we present a comprehensive theoretical study of the photophysics of heptazine and its derivative HAP-3MF. The calculations of electronic excitation energies and vibronic coupling matrix elements have been conducted at the density functional theory/multireference configuration interaction (DFT/MRCI) level of theory. We have employed a finite difference approach to determine nonadiabatic couplings and derivatives of spin–orbit coupling and electric dipole transition matrix elements with respect to normal coordinate displacements. Kinetic constants for fluorescence, phosphorescence, internal conversion (IC), ISC, and RISC have been computed in the framework of a static approach. Radiative S1 ↔ S0 transitions borrow intensity mainly from optically bright E′ π → π* states, while S1 ↔ T1 (R)­ISC is mediated by E″ states of n → π* character. Test calculations show that IST gaps as large as those reported in the literature are counterproductive and slow down the S1 ← T1 RISC process. Using the adiabatic DFT/MRCI singlet–triplet splitting of −0.02 eV, we find vibronically enhanced ISC and RISC to be fast in the heptazine core compound. Nevertheless, its photo- and electroluminescence quantum yields are predicted to be very low because S1 → S0 IC efficiently quenches the luminescence. In contrast, fluorescence, IC, ISC, and RISC proceed at similar time scales in HAP-3MF.

10-Methylisoalloxazine (MIA) and its fluorinated derivatives (6-9F-MIA) were investigated by means of quantum chemistry, looking into the influence of fluorination on fluorescence, absorption and inter-system crossing (ISC) in vacuum and in aqueous solution.

We present an efficient implementation of nonadiabatic coupling matrix elements (NACMEs) for density functional theory/multireference configuration interaction (DFT/MRCI) wave functions of singlet and triplet multiplicity and an extension of the Vibes program that allows us to determine rate constants for internal conversion (IC) in addition to intersystem crossing (ISC) nonradiative transitions. Following the suggestion of Plasser et al. [J. Chem. Theory Comput. 12, 1207 (2016)], the derivative couplings are computed as finite differences of wave function overlaps. Several measures have been taken to speed up the calculation of the NACMEs. Schur’s determinant complement is employed to build up the determinant of the full matrix of spin-blocked orbital overlaps from precomputed spin factors with fixed orbital occupation. Test calculations on formaldehyde, pyrazine, and xanthone show that the mutual excitation level of the configurations at the reference and displaced geometries can be restricted to 1. In combination with a cutoff parameter of tnorm = 10−8 for the DFT/MRCI wave function expansion, this approximation leads to substantial savings of cpu time without essential loss of precision. With regard to applications, the photoexcitation decay kinetics of xanthone in apolar media and in aqueous solution is in the focus of the present work. The results of our computational study substantiate the conjecture that S1  T2 reverse ISC outcompetes the T2 ↝ T1 IC in aqueous solution, thus explaining the occurrence of delayed fluorescence in addition to prompt fluorescence.

An acridone derivative (N-methyl-difluoro-acridone, NMA-dF) is characterized with respect to its utility as an emitter in organic light emitting diodes (OLEDs). Using steadystate and time-resolved spectroscopy as well as quantum chemistry, its ability to convert singlet and triplet excitons into light was scrutinized. NMA-dF emits in the deep blue range of the visible spectrum. Its fluorescence emission occurs with quantum yields close to 1 and a radiative rate constant of ≈5 × 10 8 s −1 . So, it processes singlet excitons very efficiently. Using 1,4-dichlorobenzene as a sensitizer, it is shown that NMA-dF also converts triplet excitons into light. With the aid of quantum chemistry, this is related to a reverse intersystem crossing starting from a higher triplet state (HIGHrISC).

This study aims at finding fluorinated flavin derivatives with modified intersystem crossing (ISC) and fluorescence properties. In total, photophysical properties of 8 derivatives were investigated computationally using combined density functional theory and multireference configuration interaction methods. On top of a screening procedure, the excited‐state decay mechanisms of selected chromophores were investigated in detail. Kinetic schemes including fluorescence, ISC as well as internal conversion (IC) channels were set up to unravel the complex excited‐state decay kinetics. We find two chromophores that exhibit promising properties with respect to fluorescence microscopy. Distinctive stabilization of the bright S1 ππ* state results in absorption in the green wavelength region and emission of (infra‐)red light. The 1(πHπL)⤳3(πH–1πL) ISC channel of the flavin chromophore was found to be deactivated upon both modifications, but nonradiative deactivation of the fluorescence by IC appears to be a problem. Alternative modifications of the pteridine dione moiety were found to result in a marked stabilization of nπ* states along with activation of El‐Sayed allowed ISC channels. For the latter two compounds, we predict fluorescence to be quenched by ISC followed by efficient population of the long‐lived T1 state via IC.