Transition-metal-based donor–acceptor systems can produce long-lived excited charge-transfer states by visible-light irradiation. The novel ruthenium­(II) polypyridyl type complexes Ru1 and Ru2 based on the dipyridophenazine ligand (L0) directly linked to 4-hydroxythiazoles of different donor strengths were synthesized and photophysically characterized. The excited-state dynamics were investigated by femtosecond-to-nanosecond transient absorption and nanosecond emission spectroscopy complemented by time-dependent density functional theory calculations. These results indicate that photoexcitation in the visible region leads to the population of both metal-to-ligand charge-transfer (1MLCT) and thiazole (tz)-induced intraligand charge-transfer (1ILCT) states. Thus, the excited-state dynamics is described by two excited-state branches, namely, the population of (i) a comparably short-lived phenazine-centered 3MLCT state (τ ≈ 150–400 ps) and (ii) a long-lived 3ILCT state (τ ≈ 40–300 ns) with excess charge density localized on the phenazine and tz moieties. Notably, the ruthenium­(II) complexes feature long-lived dual emission with lifetimes in the ranges τEm,1 ≈ 40–300 ns and τEm,2 ≈ 100–200 ns, which are attributed to emission from the 3ILCT and 3MLCT manifolds, respectively.

No abstract

A novel 4,4-difuoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) copolymer with diethynylbenzene has been synthesised, and its ability to act as a photosensitiser for the photocatalytic generation of hydrogen was investigated by time-resolved spectroscopic techniques spanning the ps-to ns-timescales. Both transient absorption and time-resolved infrared spectroscopy were used to probe the excited state dynamics of this photosensitising unit in a variety of solvents. These studies indicated how environmental factors can influence the photophysics of the BODIPY polymer. A homogeneous photocatalytic hydrogen evolution system has been developed using the BODIPY copolymer and cobaloxime which provides hydrogen evolution rates of 319 µmol h −1 g −1 after 24 h of visible irradiation.

We report the synthesis and photophysical properties of a neutral BODIPY photosensitizing copolymer (poly-8-(4-hydroxymethylphenyl)-4,4-difluoro-2,6-diethynyl-4-bora-3a,4a-diaza- s -indacene) containing ethynylbenzene links between the BODIPY units. The copolymer absorbs further towards the red in the UV-vis spectrum compared to the BODIPY precursor. Photolysis of the polymer produces a singlet excited state which crosses to the triplet surface in less than 300 ps. This triplet state was used to form singlet oxygen with a quantum yield of 0.34. The steps leading to population of the triplet state were studied using time-resolved spectroscopic techniques spanning the pico- to nanosecond timescales. The ability of the BODIPY polymer to generate a biocidal species for bactericidal activity in both solution- and coating-based studies was assessed. When the BODIPY copolymer was dropcast onto a surface, 4 log and 6 log reductions in colony forming units/ml representative of Gram-positive and Gram-negative bacteria, respectively, under illumination at 525 nm were observed. The potent broad-spectrum antimicrobial activity of a neutral metal-free copolymer when exposed to visible light conditions may have potential clinical applications in infection management.