RESUMEN
The bromine-lithium exchange-borylation-Suzuki sequence efficiently furnishes phenothiazine-terephthalonitrile donor-acceptor dyads and triads in high yields. In contrast to most phenothiazine-acceptor conjugates the title compounds are ligated in p-position to the phenothiazine nitrogen atom. Moreover, the acceptors are either directly linked or ligated by an arylene bridge and p-anisyl N-substituents on the phenothiazine are chosen to lock the tricycle into an intra-configuration. Cyclic voltammetry reveals effects of bridging and ligation of the N-substituent. Optical spectroscopy likewise displays similar band gaps, large Stokes shifts and substantial to high quantum yields in solution, in the solid state and in PMMA matrix. Time-resolved fluorescence spectroscopy indicates quite long fluorescence decay times in solution and emission components in the microsecond time range. TADF properties are further assessed by fluorescence increase in deoxygenated solution, gated emission spectroscopy and temperature-dependent determination of phosphorescence. The nature of the electronically excited states is investigated by DFT/MRCI. While for the directly ligated dyad a singlet-triplet energy gap Δ E ( S 1 - T 1 ) ${{E}_{{({\rm S}}_{1}-{{\rm T}}_{1})}{\rm \ }}$ of 0.24â eV can be estimated and is consistently confirmed by quantum chemical calculations on the lowest energy conformer, even lower Δ E ( S 1 - T 1 ) ${{\rm \Delta }{E}_{{(S}_{1}-{T}_{1})}{\rm \ }}$ of 0.029 and 0.008â eV are estimated for the investigated dyads and the triad in the solid state and in PMMA matrix.
RESUMEN
Differently 5-substituted 8-methoxypsoralens can be synthesized by an efficient synthetic route with various cross-coupling methodologies, such as Suzuki, Sonogashira and Heck reaction. Compared to previously synthesized psoralens, thereby promising daylight absorbing compounds as potentially active agents against certain skin diseases can be readily accessed. Extensive investigations of all synthesized psoralen derivatives reveal fluorescence in the solid state as well as several distinctly emissive derivatives in solution. Donor-substituted psoralens exhibit remarkable photophysical properties, such as high fluorescence quantum yields and pronounced emission solvatochromicity and acidochromicity, which were scrutinized by Lippert-Mataga and Stern-Volmer plots. The results indicate that the compounds exceed the limit of visible light, a significant factor for potential applications as an active agent. In addition, (TD)DFT calculations were performed to elucidate the underlying electronic structure and to assign experimentally obtained data.
RESUMEN
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.