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We report the synthesis and photophysical characterization of novel halogenated dipyrrolonaphthyridine‐diones (X₂–DPNDs, X = Cl, Br, and I), as candidates for photodynamic therapy (PDT) application. Apart from the heavy atom‐induced spin‐orbit coupling (SOC) dynamics in the investigated X₂–DPNDs, it was found that the position of the halogen atom (relative to the nitrogen of the pyrrole ring) also influenced the triplet excited state behavior. Interestingly, the faster/efficiency sensitization of³O₂to¹O₂using X₂–DPND correlates with the rate of triplet population,k_ISC >1.6 × 10⁸s⁻¹for I₂–DPNDvs k_ISC >2.9 × 10⁹s⁻¹for Cl₂–DPND and Br₂–DPND (whereτ_ISC = 343 ± 3 ps for I₂–DPND andτ_ISC = 5–6 ns for Cl₂–DPND and Br₂–DPND are the lowest time constants/values for ISC). Furthermore, the heavy atom‐induced SOC in Cl₂–DPND and Br₂–DPND did not lead to a reduction of the corresponding fluorescence (ca75%vs67% for the parent DPND). The attractive photophysical characteristics of Cl₂/Br₂–DPND put them on the landscape as not only promising PDT agents but also as fluorescence probes. The present study is a stepping stone in the development of novel organic photosystems for synergistic photomedicinal applications.

 

We report two new organic green‐absorbing singlet oxygen (¹O₂) photosensitizers: Quinoidal naphthyl thioamide (QDM) andbis‐iodol‐dipyrrolonaphthyridine‐dione (I₂–DPND), with triplet energies of 40.8 and 47.5 kcal mol⁻¹(at 77 K in a glassy matrix) , respectively. The UV–vis absorption and emission characteristics ofQDMandI₂–DPNDare similar to other commercially available organic¹O₂photosensitizers such as Rose Bengal, which was used as standard/reference to estimate the¹O₂quantum yield (Φ_∆) of the chromophores under study. Using 9,10‐diphenylanthracene (DPA) as an¹O₂quencher, we estimated the Φ_∆≈ 67–85% forQDMand Φ_∆≈ 25–32% forI₂–DPND. The discrepancy in the Φ_∆values could be explained by the apparent photo‐decomposition of the later dye. Nevertheless, the high Φ_∆value forQDMis unprecedented, as this chromophore exhibits relatively low structural complexity and could further be derivatized to create novel photodynamic agents.

 

The design/synthesis and characterization of organic donor–acceptor (D–A) dyads can provide precious data allowing to improve the efficiency of classical photo-induced bimolecular interactions/processes. In this report, two novel triplet D–A dyads (4 and 5) were synthesized and fully characterized. While the optical absorption and emission profiles of these new systems exhibit similar spectral structures as that of the triplet donor/sensitizer quinoidal thioamide (QDN), the transient absorption (TA) spectra of these two dyads produced new features that can be associated with triplet transients and charge transfer species. However, the kinetics of the excited-state processes/dynamics is significantly influenced by the geometrical arrangement(s) of donor/acceptor chromophores. Further analysis of the TA data suggests that the dyad with slip-stack geometry (4) is less effective in undergoing both intra- and inter-dyad triplet energy transfer than the dyad with co-facial geometry (5). Subsequently, triplet sensitization of 9,10-diphenylanthracene (DPA) using both dyads led to upconverted photoluminescence via triplet–triplet annihilation of DPA triplet transients. But, it was found that a maximum upconversion quantum yield could be achieved at a low power density using the co-facial type dyad 5. Altogether, these results provide valuable guidance in the design of triplet donor–acceptor dyads, which could be used for light-harvesting/modulation applications.