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- ItemShape-Memory Metallopolymers Based on Two Orthogonal Metal–Ligand Interactions(Weinheim : Wiley-VCH, 2021) Meurer, Josefine; Hniopek, Julian; Bätz, Thomas; Zechel, Stefan; Enke, Marcel; Vitz, Jürgen; Schmitt, Michael; Popp, Jürgen; Hager, Martin D.; Schubert, Ulrich S.A new shape-memory polymer is presented, in which both the stable phase as well as the switching unit consist of two different metal complexes. Suitable metal ions, which simultaneously form labile complexes with histidine and stable ones with terpyridine ligands, are identified via isothermal titration calorimetry (ITC) measurements. Different copolymers are synthesized, which contain butyl methacrylate as the main monomer and the metal-binding ligands in the side chains. Zn(TFMS)2 and NiCl2 are utilized for the dual crosslinking, resulting in the formation of metallopolymer networks. The switching temperature can simply be tuned by changing the composition as well as by the choice of the metal ion. Strain fixity rates (about 99%) and very high strain recovery rates (up to 95%) are achieved and the mechanism is revealed using different techniques such as Raman spectroscopy. © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
- 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.
- ItemExcited-State Dynamics in Borylated Arylisoquinoline Complexes in Solution and in cellulo(Weinheim : Wiley-VCH, 2023) Yang, Tingxiang; Valavalkar, Abha; Romero‐Arenas, Antonio; Dasgupta, Anindita; Then, Patrick; Chettri, Avinash; Eggeling, Christian; Ros, Abel; Pischel, Uwe; Dietzek‐Ivanšić, BenjaminTwo four-coordinate organoboron N,C-chelate complexes with different functional terminals on the PEG chains are studied with respect to their photophysical properties within human MCF-7 cells. Their excited-state properties are characterized by time-resolved pump-probe spectroscopy and fluorescence lifetime microscopy. The excited-state relaxation dynamics of the two complexes are similar when studied in DMSO. Aggregation of the complexes with the carboxylate terminal group is observed in water. When studying the light-driven excited-state dynamics of both complexes in cellulo, i. e., after being taken up into human MCF-7 cells, both complexes show different features depending on the nature of the anchoring PEG chains. The lifetime of a characteristic intramolecular charge-transfer state is significantly shorter when studied in cellulo (360±170 ps) as compared to in DMSO (∼960 ps) at 600 nm for the complexes with an amino group. However, the kinetics of the complexes with the carboxylate group are in line with those recorded in DMSO. On the other hand, the lifetimes of the fluorescent state are almost identical for both complexes in cellulo. These findings underline the importance to evaluate the excited-state properties of fluorophores in a complex biological environment in order to fully account for intra- and intermolecular effects governing the light-induced processes in functional dyes.
- ItemPhotophysics of Anionic Bis(4H-imidazolato)CuI Complexes(Weinheim : Wiley-VCH, 2022) Seidler, Bianca; Tran, Jens H.; Hniopek, Julian; Traber, Philipp; Görls, Helmar; Gräfe, Stefanie; Schmitt, Michael; Popp, Jürgen; Schulz, Martin; Dietzek‐Ivanšić, BenjaminIn this paper, the photophysical behavior of four panchromatically absorbing, homoleptic bis(4H-imidazolato)CuI complexes, with a systematic variation in the electron-withdrawing properties of the imidazolate ligand, were studied by wavelength-dependent time-resolved femtosecond transient absorption spectroscopy. Excitation at 400, 480, and 630 nm populates metal-to-ligand charge transfer, intraligand charge transfer, and mixed-character singlet states. The pump wavelength-dependent transient absorption data were analyzed by a recently established 2D correlation approach. Data analysis revealed that all excitation conditions yield similar excited-state dynamics. Key to the excited-state relaxation is fast, sub-picosecond pseudo-Jahn-Teller distortion, which is accompanied by the relocalization of electron density onto a single ligand from the initially delocalized state at Franck-Condon geometry. Subsequent intersystem crossing to the triplet manifold is followed by a sub-100 ps decay to the ground state. The fast, nonradiative decay is rationalized by the low triplet-state energy as found by DFT calculations, which suggest perspective treatment at the strong coupling limit of the energy gap law.
- ItemQuinoline Photobasicity: Investigation within Water-Soluble Light-Responsive Copolymers(Weinheim : Wiley-VCH, 2021) Sittig, Maria; Tom, Jessica C.; Elter, Johanna K.; Schacher, Felix H.; Dietzek, BenjaminQuinoline photobases exhibit a distinctly higher pKa in their electronically excited state than in the ground state, thereby enabling light-controlled proton transfer reactions, for example, in molecular catalysis. The absorption of UV light translates to a pKa jump of approximately 10 units, as established for small-molecule photobases. This contribution presents the first synthesis of quinoline-based polymeric photobases prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization. The integration of quinolines as photobase chromophores within copolymers offers new possibilities for light-triggered proton transfer in nanostructured materials, that is, in nanoparticles, at surfaces, membranes and interfaces. To exploit the light-triggered reactivity of photobases within such materials, we first investigated how the ground- and excited-state properties of the quinoline unit changes upon polymer integration. To address this matter, we combined absorption and emission spectroscopy with time-resolved transient-absorption studies to reveal photoinduced proton-transfer dynamics in various solvents. The results yield important insights into the thermodynamic and kinetic properties of these polymeric quinoline photobases. © 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH
- Item1,7,9,10-Tetrasubstituted PMIs Accessible through Decarboxylative Bromination: Synthesis, Characterization, Photophysical Studies, and Hydrogen Evolution Catalysis(Weinheim : Wiley-VCH, 2020) Costabel, Daniel; Skabeev, Artem; Nabiyan, Afshin; Luo, Yusen; Max, Johannes B.; Rajagopal, Ashwene; Kowalczyk, Daniel; Dietzek, Benjamin; Wächtler, Maria; Görls, Helmar; Ziegenbalg, Dirk; Zagranyarski, Yulian; Streb, Carsten; Schacher, Felix H.; Peneva, KalinaIn this work, we present a new synthetic strategy for fourfold-substituted perylene monoimides via tetrabrominated perylene monoanhydrides. X-ray diffraction analysis unveiled the intramolecular stacking orientation between the substituents and semicircular packing behavior. We observed the remarkable influence of the substituent on the longevity and nature of the excited state upon visible light excitation. In the presence of poly(dehydroalanine)-graft-poly(ethylene glycol) graft copolymers as solubilizing template, the chromophores are capable of sensitizing [Mo3S13]2− clusters in aqueous solution for stable visible light driven hydrogen evolution over three days. © 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH
- ItemIntracellular Photophysics of an Osmium Complex bearing an Oligothiophene Extended Ligand(Weinheim : Wiley-VCH, 2020) Schneider, Kilian R.A.; Chettri, Avinash; Cole, Houston D.; Reglinski, Katharina; Breckmann, Jannik; Roque, John A. III; Stumper, Anne; Nauroozi, Djawed; Schmid, Sylvia; Lagerholm, Christoffer B.; Rau, Sven; Bäuerle, Peter; Eggeling, Christian; Cameron, Colin G.; McFarland, Sherri A.; Dietzek, BenjaminThis contribution describes the excited-state properties of an Osmium-complex when taken up into human cells. The complex 1 [Os(bpy)2(IP-4T)](PF6)2 with bpy=2,2′-bipyridine and IP-4T=2-{5′-[3′,4′-diethyl-(2,2′-bithien-5-yl)]-3,4-diethyl-2,2′-bithiophene}imidazo[4,5-f][1,10]phenanthroline) can be discussed as a candidate for photodynamic therapy in the biological red/NIR window. The complex is taken up by MCF7 cells and localizes rather homogeneously within in the cytoplasm. To detail the sub-ns photophysics of 1, comparative transient absorption measurements were carried out in different solvents to derive a model of the photoinduced processes. Key to rationalize the excited-state relaxation is a long-lived 3ILCT state associated with the oligothiophene chain. This model was then tested with the complex internalized into MCF7 cells, since the intracellular environment has long been suspected to take big influence on the excited state properties. In our study of 1 in cells, we were able to show that, though the overall model remained the same, the excited-state dynamics are affected strongly by the intracellular environment. Our study represents the first in depth correlation towards ex-vivo and in vivo ultrafast spectroscopy for a possible photodrug. © 2020 The Authors. Published by Wiley-VCH GmbH
- ItemCovalent Linkage of BODIPY-Photosensitizers to Anderson-Type Polyoxometalates Using CLICK Chemistry(Weinheim : Wiley-VCH, 2021) Cetindere, Seda; Clausing, Simon T.; Anjass, Montaha; Luo, Yusen; Kupfer, Stephan; Dietzek, Benjamin; Streb, CarstenThe covalent attachment of molecular photosensitizers (PS) to polyoxometalates (POMs) opens new pathways to PS-POM dyads for light-driven charge-transfer and charge-storage. Here, we report a synthetic route for the covalent linkage of BODIPY-dyes to Anderson-type polyoxomolybdates by using CLICK chemistry (i. e. copper-catalyzed azide-alkyne cycloaddition, CuAAC). Photophysical properties of the dyad were investigated by combined experimental and theoretical methods and highlight the role of both sub-components for the charge-separation properties. The study demonstrates how CLICK chemistry can be used for the versatile linkage of organic functional units to molecular metal oxide clusters. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH
- ItemMicrowave-Assisted Synthesis of Core–Shell Nanoparticles—Insights into the Growth of Different Geometries(Weinheim : Wiley-VCH, 2020) Womiloju, Aisha A.; Höppener, Christiane; Schubert, Ulrich S.; Hoeppener, StephanieMicrowave irradiation is utilized for the rapid synthesis of gold–silver core–shell bimetallic nanoparticles (NPs) in a two-step process. A strategy of establishing a bilayer organic barrier around the core using citrate and ascorbic acid as capping agents, providing a means to achieve a well-defined boundary layer between the core and the shell material, is reported. These boundary layers are essential for synthesizing different core–shell morphologies and the approach results in tunable bimetallic NPs with defined core–shell structures, both for spherical as well as for triangular seed cores. In addition, theoretical calculations of the plasmonic characteristics based on the boundary element method of different classes of NPs are conducted. These investigations enable conclusions to be drawn on the influence of the core morphology on the tunability of their localized surface plasmon resonances. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemScalable Functionalization of Optical Fibers Using Atomically Thin Semiconductors(Weinheim : Wiley-VCH Verlag, 2020) Ngo G.Q.; George A.; Schock R.T.K.; Tuniz A.; Najafidehaghani E.; Gan Z.; Geib N.C.; Bucher T.; Knopf H.; Saravi S.; Neumann C.; Lühder T.; Schartner E.P.; Warren-Smith S.C.; Ebendorff-Heidepriem H.; Pertsch T.; Schmidt M.A.; Turchanin A.; Eilenberger F.Atomically thin transition metal dichalcogenides are highly promising for integrated optoelectronic and photonic systems due to their exciton-driven linear and nonlinear interactions with light. Integrating them into optical fibers yields novel opportunities in optical communication, remote sensing, and all-fiber optoelectronics. However, the scalable and reproducible deposition of high-quality monolayers on optical fibers is a challenge. Here, the chemical vapor deposition of monolayer MoS2 and WS2 crystals on the core of microstructured exposed-core optical fibers and their interaction with the fibers’ guided modes are reported. Two distinct application possibilities of 2D-functionalized waveguides to exemplify their potential are demonstrated. First, the excitonic 2D material photoluminescence is simultaneously excited and collected with the fiber modes, opening a novel route to remote sensing. Then it is shown that third-harmonic generation is modified by the highly localized nonlinear polarization of the monolayers, yielding a new avenue to tailor nonlinear optical processes in fibers. It is anticipated that the results may lead to significant advances in optical-fiber-based technologies. © 2020 The Authors. Published by Wiley-VCH GmbH