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91.
Highly Luminescent Cesium Lead Halide Perovskite Nanocrystals with Tunable Composition and Thickness by Ultrasonication 下载免费PDF全文
Yu Tong Eva Bladt Meltem F. Aygüler Aurora Manzi Dr. Karolina Z. Milowska Verena A. Hintermayr Prof. Dr. Pablo Docampo Prof. Dr. Sara Bals Dr. Alexander S. Urban Dr. Lakshminarayana Polavarapu Prof. Dr. Jochen Feldmann 《Angewandte Chemie (International ed. in English)》2016,55(44):13887-13892
We describe the simple, scalable, single‐step, and polar‐solvent‐free synthesis of high‐quality colloidal CsPbX3 (X=Cl, Br, and I) perovskite nanocrystals (NCs) with tunable halide ion composition and thickness by direct ultrasonication of the corresponding precursor solutions in the presence of organic capping molecules. High angle annular dark field scanning transmission electron microscopy (HAADF‐STEM) revealed the cubic crystal structure and surface termination of the NCs with atomic resolution. The NCs exhibit high photoluminescence quantum yields, narrow emission line widths, and considerable air stability. Furthermore, we investigated the quantum size effects in CsPbBr3 and CsPbI3 nanoplatelets by tuning their thickness down to only three to six monolayers. The high quality of the prepared NCs (CsPbBr3) was confirmed by amplified spontaneous emission with low thresholds. The versatility of this synthesis approach was demonstrated by synthesizing different perovskite NCs. 相似文献
92.
Dennis Jansen Johannes Gramüller Felix Niemeyer Torsten Schaller Matthias C. Letzel Stefan Grimme Hui Zhu Ruth M. Gschwind Jochen Niemeyer 《Chemical science》2020,11(17):4381
Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst–catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which reacts mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid–acid interactions have a drastic influence on the reaction rate and stereoselectivity of asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids.Supramolecular acid–acid interactions lead to competing monomeric and dimeric pathways in phosphoric acid catalysis – so that stereoselectivities depend on catalyst concentration. 相似文献
93.
Dr. Joydev Hatai Dr. Christoph Hirschhäuser Prof. Dr. Carsten Schmuck Dr. Jochen Niemeyer 《ChemistryOpen》2020,9(7):786-792
A coumarin based probe for the efficient detection of hydrogen sulfide in aqueous medium is reported. The investigated coumarine-based derivative forms spherical nanoparticles in aqueous media. In presence of Pd2+, a metallosupramolecular coordination polymer is formed, which is accompanied by quenching of the coumarin emission at 390 nm. Its Pd2+ complex could be used as a probe for chemoselective detection of monohydrogensulfide (HS−). Presence of HS− leads to a'turn-on' fluorescence signal, resulting from decomplexation of Pd2+ from the metallosupramolecular probe. The probe was successfully applied for qualitative and quantitative detection of HS− in different sources of water directly collected from sea, river, tap and laboratory drain water, as well as in growth media for aquatic species. 相似文献
94.
The structure and dynamics of the adsorbate CO(2)/KCl(100) from a diluted phase to a saturated monolayer have been investigated with He atom scattering (HAS), low-energy electron diffraction (LEED), and polarization dependent infrared spectroscopy (PIRS). Two adsorbate phases with different CO(2) coverage have been found. The low-coverage phase is disordered at temperatures near 80 K and becomes at least partially ordered at lower temperatures, characterized by a (2√2×√2)R45° diffraction pattern. The saturated 2D phase has a high long-range order and exhibits (6√2×√2)R45° symmetry. Its isosteric heat of adsorption is 26 ± 4 kJ mol(-1). According to PIRS, the molecules are oriented nearly parallel to the surface, the average tilt angle in the saturated monolayer phase is 10° with respect to the surface plane. For both phases, structure models are proposed by means of potential calculations. For the saturated monolayer phase, a striped herringbone structure with 12 inequivalent molecules is deduced. The simulation of infrared spectra based on the proposed structures and the vibrational exciton approach gives reasonable agreement between experimental and simulated infrared spectra. 相似文献
95.
The need for new isotope reference materials 总被引:1,自引:0,他引:1
Jochen Vogl Martin Rosner Wolfgang Pritzkow 《Analytical and bioanalytical chemistry》2013,405(9):2763-2770
Isotope reference materials are needed to calibrate and validate analytical procedures used for the determination of isotope amount ratios, procedurally defined isotope ratios or so-called δ values. In contrast to the huge analytical progress in isotope ratio analytics, the production of isotope reference materials has not kept pace with the increasing needs of isotope analysts. Three representative isotope systems are used to explain the technical and non-technical difficulties and drawbacks, on one hand, and to demonstrate what can be achieved at its best, on the other hand. A clear statement is given that new isotope reference materials are needed to obtain traceable and thus comparable data, which is essential for all kinds of isotope research. The range of available isotope reference materials and δ reference materials should be increased and matrix reference materials certified for isotope compositions or δ values, which do not exist yet, should be provided. 相似文献
96.
One-bond Pt-Pt nuclear spin-spin coupling constants J(Pt-Pt) for closely related dinuclear Pt complexes can differ by an order of magnitude without any obvious correlation with Pt-Pt distances. As representative examples, the spin-spin couplings of the dinuclear Pt(I) complexes [Pt(2)(CO)(6)](2+) (1) and [Pt(2)(CO)(2)Cl(4)](2-) (2) have been computationally studied with a recently developed relativistic density functional method. The experimental values are (1)J((195)Pt-(195)Pt) = 5250 Hz for 2 but 551 Hz for 1. Many other examples are known in the literature. The experimental trends are well reproduced by the computations and can be explained based on the nature of the ligands that are coordinated to the Pt-Pt fragment. The difference for J(Pt-Pt) of an order of magnitude is caused by a sensitive interplay between the influence of different ligands on the Pt-Pt bond, and relativistic effects on metal-metal and metal-ligand bonds as well as on "atomic orbital contributions" to the nuclear spin-spin coupling constants. The results can be intuitively rationalized with the help of a simple qualitative molecular orbital diagram. 相似文献
97.
Nikolai J Loe Ø Dominiak PM Gerlitz OO Autschbach J Davies HM 《Journal of the American Chemical Society》2007,129(35):10763-10772
Quantum chemical DFT calculations at the B3LYP/6-31G(d) level have been used to study the stereochemical course of the photochemical cycloaddition of enone 9 with dienes. The observed products of this photochemically induced cycloaddition showed a stereoselectivity, which is opposite to what would be expected by FMO considerations. The quantum chemical calculations revealed that the unusual stereoselectivity of the reaction can be rationalized by assuming a stereospecific photochemical cis-trans isomerization of enone 9 to trans isomer 9a followed by a thermal Diels-Alder reaction of the diene onto the highly reactive trans enone. The photochemical reaction step involves the selective formation of a twisted triplet intermediate, which accounts for the selectivity of the reaction. 相似文献
98.
Crystal Structures of TMEDA Adducts and of Salts with Protonated TMEDA Molecules The reaction of TMEDA with two equivalents of [BH3(SMe2)] in toluene at 20 °C gives the adduct [TMEDA(BH3)2] ( 1 ). A similar reaction of pyrrolidine with [BH3(SMe2)] in a molar ratio of 1:1 leads to the adduct [pyrrolidine(BH3)] ( 2 ). TMEDA can be introduced into the coordination sphere of In3+ by the treatment of InI3 with TMEDA in toluene to give the complex [InI(TMEDA)] ( 3 ). The salt [HTMEDA]I ( 4 ), containing a mono‐protonated TMEDA molecule, is the result of the reprotonation of [NH4]I and TMEDA in toluene at 20 °C. The salts [H2TMEDA]—[InCl4(TMEDA)]2 ( 5 ) and [H2TMEDA][InCl5(THF)] ( 6 ) are formed in the reaction mixtures TMEDA/toluene/InCl3/HCl and TMEDA/toluene/THF/InCl3/HCl, respectively, whereupon 6 was characterized more closely. Crystals of [In5I6(OH)(TMEDA)4]I·2, 5toluene ( 7 ·2.5toluene) can be obtained after treatment of InI3 with non‐dried TMEDA; 4 was identifed as by‐product. 1 — 7 ·2.5toluene were partially investigated by NMR methods and vibrational spectroscopy. In all cases a characterization by single crystal X‐ray diffraction was performed. According to this, all nitrogen atoms in 1 and 2 are coordinated by BH3 groups leading to a distorted tetrahedral environment at the nitrogen and the boron atoms. In 3 a distorted trigonal‐bipyramidal coordination sphere at the In3+ is present. The apical positions are occupied by I3 and N3. Strong N‐H···N bridges, running along [001] is the feature in 4 ; the I—‐Ions are not involved into the system of H‐bridges. A ion triple, [H2TMEDA][InCl4(TMEDA)]2, hold together by bifurcated H‐bridges is the dominating structural motif in 5 , whereas alternation bifurcated and linear H‐bridges, leading zu a zig‐zag chain along [100], is the build‐up principle of 6 . In 7 ·2.5toluene a complex In5O8 skeleton was formed, consisting of a virtual corner‐connected doubled heterocubane. At every heterocubane a corner, occupied by a metal ion, is missing. The coordination spheres of the In atoms of the complex cation are completed by TMEDA molecules and iodide ions. 相似文献
99.
100.
In 1907 Lord Rayleigh published a paper on the dynamic theory of gratings. In this paper he presented a rigorous approach for solving plane wave scattering on periodic surfaces. Moreover he derived explicit expressions for a perfectly conducting sinusoidal surface, and for perpendicular incidence of the electromagnetic plane wave. This paper was criticized by Lippmann in 1953 for he assumed Rayleigh’s approach to be incomplete. Since this time there have been published several arguments, proofs, and discussions concerning the correctness and the range of validity of Rayleigh’s approach not only for plane wave scattering on gratings but also for light scattering on nonspherical structures, in general. In the paper at hand we will discuss the different point of views on what is called “Rayleigh’s hypothesis” as well as the relevance of a found theoretical limit for its validity. Furthermore we present a numerical treatment of the original scattering problem of a p-polarized plane wave perpendicularly incident on a perfectly conducting sinusoidal surface (i.e., the scalar Dirichlet problem). In doing so we emphasizes the near-field solution especially within the grooves of the grating up to points on the surface, and below the surface. Two different Green’s function formulations of Huygens’ principle are used as starting points. One of this formulation results in the general T-matrix approach which is considered to be affected by Rayleigh’s hypothesis especially for near-field calculations. The other formulation provides a conventional boundary integral equation which is in accordance with Lippmann’s point of view and free of problems with Rayleigh’s hypothesis. But the obtained results show that Lippmann’s argumentation do not withstand a critical numerical analysis, and that the independence of least-squares approaches from Rayleigh’s hypothesis, as understood and proven by Millar, seems to hold also for certain methods which does not fit into such an approach. 相似文献