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111.
Dr. Adrián Leandro Lewandowski Dr. Sergio Tosoni Leonard Gura Dr. Zechao Yang Dr. Alexander Fuhrich Dr. Mauricio J. Prieto Dr. Thomas Schmidt Dr. Denis Usvyat Prof. Wolf-Dieter Schneider Dr. Markus Heyde Prof. Gianfranco Pacchioni Prof. Hans-Joachim Freund 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):1870-1885
The present review reports on the preparation and atomic-scale characterization of the thinnest possible films of the glass-forming materials silica and germania. To this end state-of-the-art surface science techniques, in particular scanning probe microscopy, and density functional theory calculations have been employed. The investigated films range from monolayer to bilayer coverage where both, the crystalline and the amorphous films, contain characteristic XO4 (X=Si,Ge) building blocks. A side-by-side comparison of silica and germania monolayer, zigzag phase and bilayer films supported on Mo(112), Ru(0001), Pt(111), and Au(111) leads to a more general comprehension of the network structure of glass former materials. This allows us to understand the crucial role of the metal support for the pathway from crystalline to amorphous ultrathin film growth. 相似文献
112.
Andrey Shatskiy Anton Axelsson Elena V. Stepanova Jian-Quan Liu Azamat Z. Temerdashev Bhushan P. Kore Bjrn Blomkvist James M. Gardner Peter Dinr Markus D. Krks 《Chemical science》2021,12(15):5430
A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids. The developed protocol allows the use of ubiquitous carboxylic acids as radical precursors without prior derivatization. The protocol utilizes near-stoichiometric amounts of the imine and the acid radical precursor in combination with a catalytic amount of an organic acridinium-based photocatalyst. Alternative mechanisms for the developed transformation are discussed and corroborated by experimental and computational studies.A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids. 相似文献
113.
Markus Kury Katharina Ehrmann György Attila Harakály Christian Gorsche Robert Liska 《Journal of polymer science. Part A, Polymer chemistry》2021,59(19):2154-2169
In the last decades the importance of UV curable formulations has increased continuously. Their fast curing speed, solvent-free polymerization conditions, and the formation of hard and highly crosslinked photopolymer networks represent major benefits. Commercial UV resins generally consist of multi-functional vinyl oligomers, photoinitiators, additives, and reactive diluents. Mono- and multi-functional reactive diluents serve as thinners to lower the overall resin viscosity and to improve processability. However, many monofunctional reactive diluents like isobornyl (meth)acrylate or benzyl (meth)acrylate exhibit high volatility, often already at room temperature. This causes adverse effects such as unpleasant odor, potential health risks, and changing resin composition during processing. A new group of monomers that show high potential for replacing traditional highly volatile reactive diluents are salicylate (meth)acrylates. In this work, salicylate-based thinners are synthesized, polymerized, and characterized with respect to their viscosity, volatility, thermal stability, photoreactivity, and thermomechanical properties of their homopolymers. Additionally, a first example of their diluting effect in a highly viscous difunctional polyester urethane methacrylate is demonstrated with 30 wt% of a cycloaliphatically and an aromatically substituted salicylate methacrylate. The polymers of the diluted resin exhibit similarly high glass transition temperatures of 110 and 126 °C, which are in the range of the polymers of the undiluted resin. 相似文献
114.
Stephan Schaumüller Doris Cristurean Stephan Haudum George S. Pappas Markus Himmelsbach Matthias Bechmann Oliver Brüggemann Ian Teasdale 《Journal of polymer science. Part A, Polymer chemistry》2021,59(24):3161-3166
We report a facile post-polymerization modification route to functionalized aromatic polyimides via Diels-Alder cycloaddition. Aromatic polyimides are important, versatile high-performance polymers; however, their structural diversity is restricted by the requirements of the step-growth polymerization. We prepared polyimides with alkynes in their main-chain as macromolecular dienophiles and quantitatively grafted tetraphenylcyclopentadienone based dienes. The resulting solution-processable, wholly aromatic polyimides show a considerable increase in surface area due to the induced conformational changes and bulky, rigid, and contorted molecular structures. The orthogonality of the reaction is exploited to insert functional groups, namely bromine and sulfonates, along the polymer backbone. In a further extension, the phenylene segments undergo cyclodehydrogenation to form nanographene segments within the polymer chains. The Diels-Alder cycloaddition onto polyimides is therefore demonstrated to be an effective, widely applicable route to tunable high-performance polymers with value-added functionality and thus considerable potential in a wide range of advanced materials. 相似文献
115.
Markus Bursch Lukas Kunze Dr. Amol M. Vibhute Dr. Andreas Hansen Prof. Dr. Kana M. Sureshan Dr. Peter G. Jones Prof. Dr. Stefan Grimme Prof. Dr. Daniel B. Werz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(14):4627-4639
The noncovalent interactions between azides and oxygen-containing moieties are investigated through a computational study based on experimental findings. The targeted synthesis of organic compounds with close intramolecular azide–oxygen contacts yielded six new representatives, for which X-ray structures were determined. Two of those compounds were investigated with respect to their potential conformations in the gas phase and a possible significantly shorter azide–oxygen contact. Furthermore, a set of 44 high-quality, gas-phase computational model systems with intermolecular azide–pnictogen (N, P, As, Sb), –chalcogen (O, S, Se, Te), and –halogen (F, Cl, Br, I) contacts are compiled and investigated through semiempirical quantum mechanical methods, density functional approximations, and wave function theory. A local energy decomposition (LED) analysis is applied to study the nature of the noncovalent interaction. The special role of electrostatic and London dispersion interactions is discussed in detail. London dispersion is identified as a dominant factor of the azide–donor interaction with mean London dispersion energy-interaction energy ratios of 1.3. Electrostatic contributions enhance the azide–donor coordination motif. The association energies range from −1.00 to −5.5 kcal mol−1. 相似文献
116.
Dr. Christiane Stoll Prof. Dr. Mihail Atanasov Jascha Bandemehr Prof. Dr. Frank Neese Clemens Pietzonka Prof. Dr. Florian Kraus Prof. Dr. Antti J. Karttunen Dr. Markus Seibald Assoc. Prof. Dr. Gunter Heymann Prof. Dr. Hubert Huppertz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(38):9801-9813
As a consequence of the static Jahn-Teller effect of the 5E ground state of MnIII in cubic structures with octahedral parent geometries, their octahedral coordination spheres become distorted. In the case of six fluorido ligands, [MnF6]3− anions with two longer and four shorter Mn−F bonds making elongated octahedra are usually observed. Herein, we report the synthesis of the compound K3[MnF6] through a high-temperature approach and its crystallization by a high-pressure/high-temperature route. The main structural motifs are two quasi-isolated, octahedron-like [MnF6]3− anions of quite different nature compared to that met in ideal octahedral MnIII Jahn-Teller systems. Owing to the internal electric field of Ci symmetry dominated by the next-neighbour K+ ions acting on the MnIII sites, both sites, the pseudo-rhombic (site 1) and the pseudo-tetragonally elongated (site 2) [MnF6]3− anions are present in K3[MnF6]. The compound was characterized by single-crystal and powder X-ray diffraction, and magnetometry as well as by FTIR, Raman, and ligand field spectroscopy. A theoretical interpretation of the electronic structure and molecular geometry of the two Mn sites in the lattice is given by using a vibronic coupling model with parameters adjusted from multireference ab-initio cluster calculations. 相似文献
117.
Freia Ruegenberg Dr. Markus Seibald Dr. Dominik Baumann Dr. Simon Peschke Dr. Frauke Philipp Prof. Dr. Hubert Huppertz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(45):11701-11706
In order to expand the field of alkali lithosilicates, a new representative of the substance class with a previously unknown structure type was found based on solid-state synthesis. The novel compound with the sum formula Rb[Li5Si2O7] crystallizes in the orthorhombic space group Pbcm (no. 57) with a=7.6269(3), b=9.5415(4), and c=9.4095(3) Å by means of single-crystal X-ray diffraction. The structure consists of a highly condensed lithosilicate framework, built up of corner- and edge-linked [LiO4]-tetrahedra and [Si2O7]-units, and the rubidium ions aligned in channels. Suitable crystals of the material were obtained using sealed tantalum ampoules as reaction tube at a temperature of 750 °C. The new compound was further characterized via powder diffraction, Rietveld analysis, and EDX measurements. At first glance, Eu2+-doped Rb[Li5Si2O7] reveals an intense green luminescence. In-depth crystal analysis shows that a core-shell formation is present even for apparently high quality single-crystals. As a minority phase, the known green phosphor RbLi[Li3SiO4]2:Eu2+ is the origin of the luminescence, representing a tiny core inside of the particles surrounded by a large matrix of transparent Rb[Li5Si2O7] dominating the single-crystal diffraction pattern. 相似文献
118.
Loffhagen Detlef Becker Markus M. Czerny Andreas K. Klages Claus-Peter 《Plasma Chemistry and Plasma Processing》2021,41(1):289-334
Plasma Chemistry and Plasma Processing - A time-dependent, spatially one-dimensional fluid-Poisson model is applied to analyze the impact of small amounts of tetramethylsilane (TMS) as precursor on... 相似文献
119.
Berthold Fischer Helmut W. Schmalle Markus R. Baumgartner Max Viscontini 《Helvetica chimica acta》1997,80(1):103-110
The first crystal structure of a molybdenum complex 9 with a hydrogenated pterin and a sulfur ligand contributes to the discussion about the active center of molybdenum and tungsten enzymes containing a molybdopterin cofactor. Complex 9 was synthesized through a redox reaction of [MoVIO2 (LN-S2)] ( 8 ; LN-S2 = pyridine-2, 6-bis(methanethiolato)) with 5, 6, 7, 8-tetrahydropterin ( 7 ). 2 HCl (H4Ptr.2 HCl). The complex crystallizes, with a non-coordinating Cl-atom acting as a counterion, in the monoclinic space group C2/c (No. 15) with cell dimensions a = 22.900(5), b = 10.716(2), c = 17.551(4) Å, β = 120.36(3)°, and Z = 8. We interpret 9 as [MoIVO(LN-S2)(H+-q-H2Ptr)]Cl (q = quinonoid; H2Ptr = dihydropterin), i.e., a MoIV monooxo center coordinated by a pyridine-2, 6-bis(methanethiolato) ligand and a protonated dihydropterin. The spectroscopic properties of this new complex are comparable to those of other crystalline molybdenum complexes of hydrogenated pterins without additional S-coordination. The slightly H2O-soluble complex 9 reacts with the natural enzyme substrate DMSO very slowly, possibly due to the lack of easily dissociable ligands at the metal center. 相似文献
120.
Jean-Franjois Nierengarten Andreas Herrmann Rik R. Tykwinski Markus Riittimann Francois Diederich Corinne Boudon Jean-Paul Gisselbrecht Maurice Gross 《Helvetica chimica acta》1997,80(1):293-316
The synthesis of (E)-hex-3-ene-l, 5-diynes and 3-methylidenepenta-1, 4-diynes with pendant methano[60]-fullerene moieties as precursors to C60-substituted poly(triacetylenes) (PTAs, Fig. 1) and expanded radialenes (Fig. 2) is described. The Bingel reaction of diethyl (E)-2, 3-dialkynylbut-2-ene-1, 4-diyl bis(2-bromopropane-dioates) 5 and 6 with two C60 molecules (Scheme 2) afforded the monomeric, silyl-protected PTA precursors 9 and 10 which, however, could not be effectively desilylated (Scheme 4). Also formed during the synthesis of 9 and 10 , as well as during the reaction of C60 with thedesilylated analogue 16 (Scheme 5 ), were the macrocyclic products 11, 12 , and 17 , respectively, resulting from double Bingel addition to one C-sphere. Rigorous analysis revealed that this novel macrocyclization reaction proceeds with complete regio- and diastereoselectivity. The second approach to a suitable PTA monomer attempted N, N′-dicyclohexylcarbodiimide(DCC)-mediated esterification of (E)-2, 3-diethynylbut-2-ene-l, 4-diol ( 18 , Scheme 6) with mono-esterified methanofullerene-dicarboxylic acid 23 ; however, this synthesis yielded only the corresponding decarboxylated methanofullerene-carboxylic ester 27 (Scheme 7). To prevent decarboxylation, a spacer was inserted between the reacting carboxylic-acid moiety and the methane C-atom in carboxymethyl ethyl 1, 2-methano[60]fullerene-61, 61-dicarboxylate ( 28 , Scheme 8), and DCC-mediated esterification with diol 18 afforded PTA monomer 32 in good yield. The formation of a suitable monomeric precursor 38 to C60-substituted expanded radialenes was achieved in 5 steps starting from dihydroxyacetone (Schemes 9 and 10), with the final step consisting of the DCC-mediated esterification of 28 with 2-[1-ethynyl(prop-2-ynylidene)]propane-1, 3-diol ( 33 ). The first mixed C60-C70 fullerene derivative 49 , consisting of two methano[60]fullerenes attached to a methano[70]fullerene, was also prepared and fully characterized (Scheme 13). The Cs-symmetrical hybrid compound was obtained by DCC-mediated esterification of bis[2-(2-hydroxy-ethoxy)ethyl] 1, 2-methano[70]fullerene-71, 71-dicarboxylate ( 46 ) with an excess of the C60-carboxylic acid 28 . The presence of two different fullerenes in the same molecule was reflected by its UV/VIS spectrum, which displayed the characteristic absorption bands of both the C70 and C60 mono-adducts, but at the same time indicated no electronic interaction between the different fullerene moieties. Cyclic voltammetry showed two reversible reduction steps for 49 , and comparison with the corresponding C70 and C60 mono-adducts 46 and 30 indicated that the three fullerenes in the composite fullerene compound behave as independent redox centers. 相似文献