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- ItemYield—not only Lifetime—of the Photoinduced Charge-Separated State in Iridium Complex–Polyoxometalate Dyads Impact Their Hydrogen Evolution Reactivity(Weinheim : Wiley-VCH, 2020) Luo, Yusen; Maloul, Salam; Schönweiz, Stefanie; Wächtler, Maria; Streb, Carsten; Dietzek, BenjaminCovalently linked photosensitizer–polyoxometalate (PS-POM) dyads are promising molecular systems for light-induced energy conversion processes, such as “solar” hydrogen generation. To date, very little is known of their fundamental photophysical properties which affect the catalytic reactivity and stability of the systems. PS-POM dyads often feature short-lived photoinduced charge-separated states, and the lifetimes of these states are considered crucial for the function of PS-POM dyads in molecular photocatalysis. Hence, strategies have been developed to extend the lifetimes of the photoinduced charge-separated states, either by tuning the PS photophysics or by tuning the POM redox properties. Recently, some of us reported PS-POM dyads based on cyclometalated IrIII complexes covalently linked to Anderson-type polyoxometalate. Distinct hydrogen evolution reactivity (HER) of the dyads was observed, which was tuned by varying the central metal ion M of the POMM (M=Mn3+, Co3+, Fe3+). In this manuscript, the photoinduced electron-transfer processes in the three Ir-POMM dyads are investigated to rationalize the underlying reasons for the differences in HER activity observed. We report that upon excitation of the IrIII complex, ultrafast (sub-ps) charge separation occurs, leading to different amounts of the charge-separated states (Ir.+-POMM.−) generated in the different dyads. However, in all dyads studied, the resulting Ir.+-POMM.− species are short-lived (sub-ns) when compared to reference electron acceptors (e.g. porphyrins or fullerenes) reported in the literature. The reductive quenching of Ir.+-POMM.− by a sacrificial donor, triethyl amine (1 m), to generate the intermediate Ir-POMM.− is estimated to be very efficient (70–80 %) for all dyads studied. Based on this analyses, we conclude that the yield instead of the lifetime of the Ir.+-POMM.− charge-separated state determines the catalytic capacity of the dyads investigated. This new feature in the PS-POM photophysics could lead to new design criteria for the development of novel PS-POM dyads. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemPhotophysics of BODIPY dyes as readily designable photosensitisers in light-driven proton reduction(Basel : MDPI, 2017) Dura, Laura; Wächtler, Maria; Kupfer, Stephan; Kübel, Joachim; Ahrens, Johannes; Höfler, Sebastian; Bröring, Martin; Dietzek, Benjamin; Beweries, TorstenA series of boron dipyrromethene (BODIPY) dyes was tested as photosensitisers for light-driven hydrogen evolution in combination with the complex [Pd(PPh3)Cl2]2 as a source for catalytically-active Pd nanoparticles and triethylamine as a sacrificial electron donor. In line with earlier reports, halogenated dyes showed significantly higher hydrogen production activity. All BODIPYs were fully characterised using stationary absorption and emission spectroscopy. Time-resolved spectroscopic investigations on meso-mesityl substituted compounds revealed that reduction of the photo-excited BODIPY by the sacrificial agent occurs from an excited singlet state, while, in halogenated species, long-lived triplet states are present, determining electron transfer processes from the sacrificial agent. Quantum chemical calculations performed at the time-dependent density functional level of theory indicate that the differences in the photocatalytic performance of the present series of dyes can be correlated to the varying efficiency of intersystem crossing in non-halogenated and halogenated species and not to alterations in the energy levels introduced upon substitution.
- ItemModified bibenzimidazole ligands as spectator ligands in photoactive molecular functional Ru-polypyridine units? Implications from spectroscopy(Cambridge : RSC, 2014) Meyer-Ilse, J.; Bauroth, S.; Bräutigam, M.; Schmitt, M.; Popp, J.; Beckert, R.; Rockstroh, N.; Pilz, T.D.; Monczak, K.; Heinemann, F.W.; Rau, S.; Dietzek, B.The photophysical properties of Ruthenium-bipyridine complexes bearing a bibenzimidazole ligand were investigated. The nitrogens on the bibenzimidazole-ligand were protected, by adding either a phenylene group or a 1,2-ethandiyl group, to remove the photophysical dependence of the complex on the protonation state of the bibenzimidazole ligand. This protection results in the bibenzimidazole ligand contributing to the MLCT transition, which is experimentally evidenced by (resonance) Raman scattering in concert with DFT calculations for a detailed mode assignment in the (resonance) Raman spectra.
- ItemPolymeric Photoacids Based on Naphthols—Design Criteria, Photostability, and Light-Mediated Release(Weinheim : Wiley-VCH, 2019) Wendler, Felix; Sittig, Maria; Tom, Jessica C.; Dietzek, Benjamin; Schacher, Felix H.The implementation of photoswitches within polymers offers an exciting toolbox in the design of light-responsive materials as irradiation can be controlled both spatially and temporally. Herein, we introduce a range of water-soluble copolymers featuring naphthol-based chromophores as photoacids in the side chain. With that, the resulting materials experience a drastic increase in acidity upon stimulation with UV light and we systematically studied how structure and distance of the photoacid from the copolymer backbone determines polymerizability, photo-response, and photostability. Briefly, we used RAFT (reversible addition–fragmentation chain transfer) polymerization to prepare copolymers consisting of nona(ethylene glycol) methyl ether methacrylate (MEO9MA) as water-soluble comonomer in combination with six different 1-naphthol-based (“N”) monomers. Thereby, we distinguish between methacrylates (NMA, NOeMA), methacrylamides (NMAm, NOeMAm), vinyl naphthol (VN), and post-polymerization modification based on [(1-hydroxynaphthalen-2-amido)ethyl]amine (NOeMAm, NAmeMAm). These P(MEO9MAx-co-“N”y) copolymers typically feature a 4:1 MEO9MA to “N” ratio and molar masses in the range of 10 kg mol−1. After synthesis and characterization by using NMR spectroscopy and size exclusion chromatography (SEC), we investigated how potential photo-cleavage or photo-degradation during irradiation depends on the type and distance of the linker to the copolymeric backbone and whether reversible excited state proton transfer (ESPT) occurs under these conditions. In our opinion, such materials will be strong assets as light-mediated proton sources in nanostructured environments, for example, for the site-specific creation of proton gradients. We therefore exemplarily incorporated NMA into an amphiphilic block copolymer and could demonstrate the light-mediated release of Nile red from micelles formed in water as selective solvent. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.