RESUMO
The photophysics of a thermally activated delayed fluorescence (TADF) emitting macrocycle consisting of two dibenzo[a,j]phenazine acceptor moieties bridged by two N,N,N',N'-tetraphenylene-1,4-diamine donor units was scrutinized in solution by steady-state and time-resolved spectroscopy. The fluorescence lifetime of the compound proved to be strongly solvent-dependent. It ranges from 6.3â ns in cyclohexane to 34â ps in dimethyl sulfoxide. In polar solvents the fluorescence decay is predominantly due to internal conversion. In non-polar ones radiative decay and intersystem crossing contribute. Contrary to the behaviour in polymer matrices (S. Izumi et al., J. Am. Chem. Soc. 2020, 142, 1482) the excited state decay is not predominantly due to prompt and delayed fluorescence. The solvent-dependent behaviour is analyzed with the aid of quantum chemical computations.
RESUMO
8-Methoxypsoralen (8-MOP) serves as a PUVA (psoralen + UV-A) agent in the treatment of certain skin diseases. Derivatives of 8-MOP with cationic aromatic substituents at the five positions were synthesized and characterized by steady-state, femtosecond and nanosecond spectroscopy as well as cyclic voltammetry. The aromatic substituents' positive charge increases the water solubility and the affinity toward intercalation into DNA. The aromatic substituents were supposed to lower the psoralen S1 energy and thereby suppress a photo-induced electron transfer (PET) with guanine-bearing DNA. Such a suppression of this PET is expected to increase the propensity of psoralens to photo-addition to DNA. For derivatives bearing methylpyridinium residues, femtosecond spectroscopy revealed an intramolecular PET occurring on the picosecond time scale. This PET precludes the population of the triplet state. As triplet states are the precursor state for the photo-addition to DNA, their intermolecular PET renders these derivatives ineffective in terms of PUVA. For two derivatives bearing trimethylphenylammonium moieties, such an intramolecular PET does not occur and the triplet state is populated. Surprisingly, these compounds also exhibit no PUVA activity. Based on these findings, implications for further optimization of PUVA agents are discussed.
Assuntos
Furocumarinas , DNA/química , Ficusina , Furocumarinas/química , Metoxaleno/química , ÁguaRESUMO
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 steady-state 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 × 108 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).
Assuntos
Acridonas/química , Corantes Fluorescentes/química , Cobre/químicaRESUMO
The psoralens 8-methoxypsoralen (8-MOP), 4,5',8-trimethylpsoralen (TMP) and 5-methoxypsoralen (5-MOP) find clinical application in PUVA (psoralen + UVA) therapy. PUVA treats skin diseases like psoriasis and atopic eczema. Psoralens target the DNA of cells. Upon photo-excitation psoralens bind to the DNA base thymine. This photo-binding was studied using steady-state UV/Vis and IR spectroscopy as well as nanosecond transient UV/Vis absorption. The experiments show that the photo-addition of 8-MOP and TMP involve the psoralen triplet state and a biradical intermediate. 5-MOP forms a structurally different photo-product. Its formation could not be traced by the present spectroscopic technique.
Assuntos
DNA/química , Furocumarinas/química , Metoxaleno/química , Fotoquímica/métodos , Trioxsaleno/química , Dano ao DNA , Humanos , Cinética , Preparações Farmacêuticas , Teoria Quântica , Espectrofotometria Infravermelho , Espectrofotometria Ultravioleta , Raios UltravioletaRESUMO
The photophysics of N-methylphthalimide (MP) in solution (cyclohexane, ethanol, acetonitrile, and water) was characterized by steady state as well as time resolved fluorescence and absorption spectroscopy. In all solvents the compound exhibits an unusually large Stokes shift of â¼10 000 cm-1. It is attributed to an ultrafast (<100 fs) depletion of the initially excited state, which results in the population of a weakly emitting state. Quantum chemical computations (DFT-MRCI) support this. They identify two energetically low-lying singlet ππ* excitations of different oscillator strength. Whereas the Stokes shift and thereby the ultrafast depletion of the initial excitation are hardly affected by the solvent later processes respond strongly. The fluorescence lifetime varies from â¼10 ps (cyclohexane) to â¼3 ns (water). This is attributed to a varying energetic accessibility of nπ* excitations.