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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
- 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
- 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.
- ItemComparative Analysis of Raman Signal Amplifying Effectiveness of Silver Nanostructures with Different Morphology(Basel : MDPI, 2022) Yakimchuk, Dzmitry V.; Khubezhov, Soslan A.; Prigodich, Uladzislau V.; Tishkevich, Daria I.; Trukhanov, Sergei V.; Trukhanov, Alex V.; Sivakov, Vladimir; Kaniukov, Egor Y.To increase the attractiveness of the practical application of molecular sensing methods, the experimental search for the optimal shape of silver nanostructures allowing to increase the Raman cross section by several orders of magnitude is of great interest. This paper presents a detailed study of spatially separated plasmon-active silver nanostructures grown in SiO2/Si template pores with crystallite, dendrite, and “sunflower-like” nanostructures shapes. Nile blue and 2-mercaptobenzothiazole were chosen as the model analytes for comparative evaluation of the Raman signal amplification efficiency using these structures. It was discussed the features of the structures for the enhancement of Raman intensity. Finally, we showed that silver crystals, dendrites, and “sunflower-like” nanostructures in SiO2/Si template could be used as the relevant materials for Raman signal amplification, but with different efficiency.
- 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
- ItemGiant persistent photoconductivity in monolayer MoS2 field-effect transistors(London : Nature Publishing Group, 2021) George, A.; Fistul, M.V.; Gruenewald, M.; Kaiser, D.; Lehnert, T.; Mupparapu, R.; Neumann, C.; Hübner, U.; Schaal, M.; Masurkar, N.; Arava, L.M.R.; Staude, I.; Kaiser, U.; Fritz, T.; Turchanin, A.Monolayer transition metal dichalcogenides (TMD) have numerous potential applications in ultrathin electronics and photonics. The exposure of TMD-based devices to light generates photo-carriers resulting in an enhanced conductivity, which can be effectively used, e.g., in photodetectors. If the photo-enhanced conductivity persists after removal of the irradiation, the effect is known as persistent photoconductivity (PPC). Here we show that ultraviolet light (λ = 365 nm) exposure induces an extremely long-living giant PPC (GPPC) in monolayer MoS2 (ML-MoS2) field-effect transistors (FET) with a time constant of ~30 days. Furthermore, this effect leads to a large enhancement of the conductivity up to a factor of 107. In contrast to previous studies in which the origin of the PPC was attributed to extrinsic reasons such as trapped charges in the substrate or adsorbates, we show that the GPPC arises mainly from the intrinsic properties of ML-MoS2 such as lattice defects that induce a large number of localized states in the forbidden gap. This finding is supported by a detailed experimental and theoretical study of the electric transport in TMD based FETs as well as by characterization of ML-MoS2 with scanning tunneling spectroscopy, high-resolution transmission electron microscopy, and photoluminescence measurements. The obtained results provide a basis for the defect-based engineering of the electronic and optical properties of TMDs for device applications.