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- ItemLigand electronic fine-tuning and its repercussion on the photocatalytic activity and mechanistic pathways of the copper-photocatalysed aza-Henry reaction(London : RSC Publ., 2020) Li, Chenfei; Dickson, Robert; Rockstroh, Nils; Rabeah, Jabor; Cordes, David B.; Slawin, Alexandra M.Z.; HĆ¼nemƶrder, Paul; Spannenberg, Anke; BĆ¼hl, Michael; MejĆa, Esteban; Zysman-Colman, Eli; Kamer, Paul C.J.A family of six structurally related heteroleptic copper(i) complexes of the form of [Cu(N^N)(P^P)]+ bearing a 2,9-dimethyl-1,10-phenanthroline diimine (N^N) ligand and a series of electronically tunable xantphos (P^P) ligands have been synthesized and their optoelectronic properties characterized. The reactivity of these complexes in the copper-photocatalyzed aza-Henry reaction of N-phenyltetrahydroisoquinoline was evaluated, while the related excited state kinetics were comprehensively studied. By subtlety changing the electron-donating properties of the P^P ligands with negligible structural differences, we could tailor the photoredox properties and relate them to the reactivity. Moreover, depending on the exited-state redox potential of the catalysts, the preferred mechanism can shift between reductive quenching, energy transfer and oxidative quenching pathways. A combined study of the structural modulation of copper(i) photocatalysts, optoelectronic properties and photocatalytic reactivity resulted in a clearer understanding of both the rational design of the photocatalyst and the complexity of competing photoinduced electron and energy transfer mechanisms. Ā© The Royal Society of Chemistry.
- ItemExpansion of the (BB)Ru metallacycle with coinage metal cations: Formation of B-M-Ru-B (M = Cu, Ag, Au) dimetalacyclodiboryls(Cambridge : Royal Society of Chemistry, 2018) Eleazer, B.J.; Smith, M.D.; Popov, A.A.; Peryshkov, D.V.In this work, we introduce a novel approach for the selective assembly of heterometallic complexes by unprecedented coordination of coinage metal cations to strained single ruthenium-boron bonds on a surface of icosahedral boron clusters. M(i) cations (M = Cu, Ag, and Au) insert into B-Ru bonds of the (BB)-carboryne complex of ruthenium with the formation of four-membered B-M-Ru-B metalacycles. Results of theoretical calculations suggest that bonding within these metalacycles can be best described as unusual three-center-two-electron B-MāÆRu interactions that are isolobal to B-HāÆRu borane coordination for M = Cu and Ag, or the pairs of two-center-two electron B-Au and Au-Ru interactions for M = Au. These transformations comprise the first synthetic route to exohedral coinage metal boryl complexes of icosahedral closo-{C2B10} clusters, which feature short Cu-B (2.029(2) Ć ) and Ag-B (2.182(3) Ć ) bonds and the shortest Au-B bond (2.027(2) Ć ) reported to date. The reported heterometallic complexes contain Cu(i) and Au(i) centers in uncharacteristic square-planar coordination environments. These findings pave the way to rational construction of a broader class of multimetallic architectures featuring M-B bonds.
- ItemUltrathin two-dimensional conjugated metalā organic framework single-crystalline nanosheets enabled by surfactant-assisted synthesis(Cambridge : RSC, 2020) Wang, Zhonghao; Wang, Gang; Qi, Haoyuan; Wang, Mao; Wang, Mingchao; Park, SangWook; Wang, Huaping; Yu, Minghao; Kaiser, Ute; Fery, Andreas; Zhou, Shengqiang; Dong, Renhao; Feng, XinliangTwo-dimensional conjugated metal-organic frameworks (2D c-MOFs) have recently emerged for potential applications in (opto-)electronics, chemiresistive sensing, and energy storage and conversion, due to their excellent electrical conductivity, abundant active sites, and intrinsic porous structures. However, developing ultrathin 2D c-MOF nanosheets (NSs) for facile solution processing and integration into devices remains a great challenge, mostly due to unscalable synthesis, low yield, limited lateral size and low crystallinity. Here, we report a surfactant-assisted solution synthesis toward ultrathin 2D c-MOF NSs, including HHB-Cu (HHB = hexahydroxybenzene), HHB-Ni and HHTP-Cu (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). For the first time, we achieve single-crystalline HHB-Cu(Ni) NSs featured with a thickness of 4-5 nm (ā¼8-10 layers) and a lateral size of 0.25-0.65 Ī¼m2, as well as single-crystalline HHTP-Cu NSs with a thickness of ā¼5.1 Ā± 2.6 nm (ā¼10 layers) and a lateral size of 0.002-0.02 Ī¼m2. Benefiting from the ultrathin feature, the synthetic NSs allow fast ion diffusion and high utilization of active sites. As a proof of concept, when serving as a cathode material for Li-ion storage, HHB-Cu NSs deliver a remarkable rate capability (charge within 3 min) and long-term cycling stability (90% capacity retention after 1000 cycles), superior to the corresponding bulk materials and other reported MOF cathodes. This journal is Ā© The Royal Society of Chemistry.
- ItemColloidal PbS nanoplatelets synthesized via cation exchange for electronic applications(Cambridge : RSC Publ., 2019) Sonntag, Luisa; Shamraienko, Volodymyr; Fan, Xuelin; Samadi Khoshkhoo, Mahdi; Kneppe, David; Koitzsch, Andreas; Gemming, Thomas; Hiekel, Karl; Leo, Karl; Lesnyak, Vladimir; EychmĆ¼ller, AlexanderIn this work, we present a new synthetic approach to colloidal PbS nanoplatelets (NPLs) utilizing a cation exchange (CE) strategy starting from CuS NPLs synthesized via the hot-injection method. Whereas the thickness of the resulting CuS NPLs was fixed at approx. 5 nm, the lateral size could be tuned by varying the reaction conditions, such as time from 6 to 16 h, the reaction temperature (120 Ā°C, 140 Ā°C), and the amount of copper precursor. In a second step, Cu+ cations were replaced with Pb2+ ions within the crystal lattice via CE. While the shape and the size of parental CuS platelets were preserved, the crystal structure was rearranged from hexagonal covellite to PbS galena, accompanied by the fragmentation of the monocrystalline phase into polycrystalline one. Afterwards a halide mediated ligand exchange (LE) was carried out in order to remove insulating oleic acid residues from the PbS NPL surface and to form stable dispersions in polar organic solvents enabling thin-film fabrication. Both CE and LE processes were monitored by several characterization techniques. Furthermore, we measured the electrical conductivity of the resulting PbS NPL-based films before and after LE and compared the processing in ambient to inert atmosphere. Finally, we fabricated field-effect transistors with an on/off ratio of up to 60 and linear charge carrier mobility for holes of 0.02 cm2 Vā1 sā1.
- ItemInter-granular effects at high magnetic fields of cuprate and iron chalcogenide superconducting materials(Bristol : Institute of Physics Publishing, 2019) Buchkov, K.; Valkovski, M.; Gajda, D.; Nenkov, K.; Nazarova, E.The weak links effects are one of the main challenges for effective power applications of high temperature superconducting materials. Studies of these effects help for their better understanding and subsequent improvement. An overview analysis of the intergranular properties of cuprate (Y0.8Ca0.2Ba2Cu3O7-Ī“) and iron-based chalcogenide (FeSe0.5Te0.5) polycrystalline samples was carried out, by means of series of electro-transport experiments at different magnetic fields. The temperature evolution of the Josephson coupling and intrinsic superconductivity effects for the both systems was constructed. The FeSe0.5Te0.5 compound shows very stable and superior behavior compared to Y0.8Ca0.2BCO up to the highest magnetic fields (14T) used. We have explored FeSe0.5Te0.5 Josephson weak links influence (as a non-linear process) over the resistive transition using different AC current amplitudes and applying the sensitive AC transport third harmonics technique.
- ItemCorrelations between the structure and superconducting properties of MT-YBaCuO(Bristol : IOP Publ., 2020) Prikhna, T.A.; Moshchill, V.E.; Rabier, J.; Chaud, X.; Joulain, A.; Pan, A.V.; Litskendorf, D.; Habisreuther, T.Comprehensive experimental results of fully oxidized (up to YBa2Cu3O6,9-7) melt-Textured YBaCuO materials with different microstructures are presented. These microstructures are built respectively: (1) with a high dislocations density but almost without twins (after high temperature treatment at 2 GPa) and (2) with a high twin density, but practically free from dislocations and stacking faults (after high temperature oxygenation at 10-16 MPa). It is shown that for attaining high critical current densities and fields of irreversibility (jc(H-c, 0 T)=9ā¢104 A/cm2, H irr=9.7 T at 77 K), a high twin density in YBa2Cu3O6.9-7 matrix of MT-YBCO is required. The density of twins in fully oxidized materials depends on the distances between Y2BaCuO5 inclusions, larger twin densities are related to shorter distances between inclusions. The influence of phase composition of the initial powder mixtures on the distances between Y2BaCuO5 inclusions have been characterized and discussed. Ā© Published under licence by IOP Publishing Ltd.
- ItemOn the growth of Co-doped BaFe2As2 thin films on CaF2(Bristol : IOP Publ., 2019) Langer, Marco; Meyer, Sven; Ackermann, Kai; GrĆ¼newald, Lukas; Kauffmann-Weiss, Sandra; Aswartham, Saicharan; Wurmehl, Sabine; HƤnisch, Jens; Holzapfel, BernhardThe competition between phase formation of BaF2 and Ba(Fe1-xCox)2As2 on CaF2 single crystals has been analysed. Ba(Fe0.92Co0.08)2As2 thin films have been deposited by pulsed laser deposition. X-ray diffraction, atomic force microscopy and scanning electron microscopy studies have revealed that the formation of secondary phases and misorientations as well as the growth modes of the Ba(Fe0.92Co0.08)2As2 thin films strongly depend on the growth rate. At high growth rates, formation of BaF2 is suppressed. The dependency of the Ba(Fe0.92Co0.08)2As2 lattice parameters supports the idea of fluorine diffusion into the crystal structure upon suppression of BaF2 formation similar as was proposed for FeSe1-xTex thin films on CaF2. Furthermore, a growth mode transition from a layer growth mechanism to a three-dimensional growth mode at high supersaturation has been found, suggesting similarities between the growth mechanism of iron-based superconductors and high-T c cuprate thin films. Ā© 2019 Published under licence by IOP Publishing Ltd.
- ItemTopological boundaries between helical domains as a nucleation source of skyrmions in the bulk cubic helimagnet Cu2OSeO3(College Park, MD : APS, 2022) Leonov, A.O.; Pappas, C.Cu2OSeO3 represents a unique example in the family of B20 cubic helimagnets with a tilted spiral and a low-temperature skyrmion phase arising for magnetic fields applied along the easy crystallographic (100) axes. Although the stabilization mechanism of these phases can be accounted for by cubic magnetic anisotropy, the skyrmion nucleation process is still an open question, since the stability region of the skyrmion phase displays strongly hysteretic behavior with different phase boundaries for increasing and decreasing magnetic fields. Here, we address this important point using micromagnetic simulations and come to the conclusion that skyrmion nucleation is underpinned by the reorientation of spiral domains occurring near the critical magnetic fields of the phase diagrams: HC1, the critical field of the transition between the helical and conical/tiled spiral phase, and HC2, the critical field between the conical/tiled spiral and the homogenous phase. By studying a wide variety of cases we show that domain walls may have a 3D structure. Moreover, they can carry a finite topological charge stemming from half-skyrmions (merons) also permitting along-the-field and perpendicular-to-the-field orientation. Thus, domain walls may be envisioned as nucleation source of skyrmions that can form thermodynamically stable and metastable lattices as well as skyrmion networks with misaligned skyrmion tubes. The results of numerical simulations are discussed in view of recent experimental data on chiral magnets, in particular, for the bulk cubic helimagnet Cu2OSeO3.
- ItemUltrafast structural changes in SrTiO3 due to a superconducting phase transition in a YBa2Cu3O7 top layer(College Park, MD : Institute of Physics Publishing, 2010) LĆ¼bcke, A.; Zamponi, F.; Loetzsch, R.; KƤmpfer, T.; Uschmann, I.; GroĆe, V.; Schmidl, F.; Kƶttig, T.; ThĆ¼rk, M.; Schwoerer, H.; Fƶrster, E.; Seidel, P.; Sauerbrey, R.We investigate the structural response of SrTiO3 when Cooper pairs are broken in an epitaxially grown YBa2Cu3O 7 top layer due to both heating and optical excitation. The crystal structure is investigated by static, temperaturedependent and time-resolved x-ray diffraction. In the static case, a large strain field in SrTiO3 is formed in the proximity of the onset of the superconducting phase in the top layer, suggesting a relationship between both effects. For the time-dependent studies, we likewise find a large fraction of the probed volume of the SrTiO3 substrate strained if the top layer is superconducting. Upon optical breaking of Cooper pairs, the observed width of the rocking curve is reduced and its position is slightly shifted towards smaller angles. The dynamical theory of x-ray diffraction is used to model the measured rocking curves. We find that the thickness of the strained layer is reduced by about 200 nm on a sub-ps to ps timescale, but the strain value at the interface between SrTiO3 and YBa2Cu3O7 remains unaffected. Ā© IOP Publishing Ltd and Deutsche Physikalische Gesellschaft.
- ItemEnergy and symmetry of dd excitations in undoped layered cuprates measured By Cu L3 resonant inelastic x-ray scattering(Bristol : IOP, 2011) Moretti Sala, M.; Bisogni, V.; Aruta, C.; Balestrino, G.; Berger, H.; Brookes, N.B.; De Luca, G.M.; Di Castro, D.; Grioni, M.; Guarise, M.; Medaglia, P.G.; Miletto, Granozio, F.; Minola, M.; Perna, P.; Radovic, M.; Salluzzo, M.; Schmitt, T.; Zhou, K.J.; Braicovich, L.; Ghiringhelli, G.We measured the high-resolution Cu L3 edge resonant inelastic x-ray scattering (RIXS) of undoped cuprates La2CuO4, Sr2CuO2Cl2, CaCuO2 and NdBa 2Cu3O6. The dominant spectral features were assigned to dd excitations and we extensively studied their polarization and scattering geometry dependence. In a pure ionic picture, we calculated the theoretical cross sections for those excitations and used these to fit the experimental data with excellent agreement. By doing so, we were able to determine the energy and symmetry of Cu-3d states for the four systems with unprecedented accuracy and confidence. The values of the effective parameters could be obtained for the singleion crystal field model but not for a simple two-dimensional cluster model. The firm experimental assessment of dd excitation energies carries important consequences for the physics of high-Tc superconductors. On the one hand, we found that the minimum energy of orbital excitation is always ā„ 1.4 eV, i.e. well above the mid-infrared spectral range, which leaves to magnetic excitations (up to 300 meV) a major role in Cooper pairing in cuprates. On the other hand, it has become possible to study quantitatively the effective influence of dd excitations on the superconducting gap in cuprates.