共查询到20条相似文献,搜索用时 46 毫秒
1.
Irén Simkó Christoph Schran Fabien Brieuc Csaba Fábri Oskar Asvany Stephan Schlemmer Dominik Marx Attila G. Császár 《Angewandte Chemie (International ed. in English)》2023,62(41):e202306744
Quantum mechanics dictates that nuclei must undergo some delocalization. In this work, emergence of quantum nuclear delocalization and its rovibrational fingerprints are discussed for the case of the van der Waals complex . The equilibrium structure of is planar and T-shaped, one He atom solvating the quasi-linear He−H+−He core. The dynamical structure of , in all of its bound states, is fundamentally different. As revealed by spatial distribution functions and nuclear densities, during the vibrations of the molecule the solvating He is not restricted to be in the plane defined by the instantaneously bent chomophore, but freely orbits the central proton, forming a three-dimensional torus around the chromophore. This quantum delocalization is observed for all vibrational states, the type of vibrational excitation being reflected in the topology of the nodal surfaces in the nuclear densities, showing, for example, that intramolecular bending involves excitation along the circumference of the torus. 相似文献
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Chenglong Luan Johanna Angona Arjun Bala Krishnan Manuel Corva Pouya Hosseini Markus Heidelmann Ulrich Hagemann Emmanuel Batsa Tetteh Wolfgang Schuhmann Kristina Tschulik Tong Li 《Angewandte Chemie (International ed. in English)》2023,62(28):e202305982
The role of β-CoOOH crystallographic orientations in catalytic activity for the oxygen evolution reaction (OER) remains elusive. We combine correlative electron backscatter diffraction/scanning electrochemical cell microscopy with X-ray photoelectron spectroscopy, transmission electron microscopy, and atom probe tomography to establish the structure–activity relationships of various faceted β-CoOOH formed on a Co microelectrode under OER conditions. We reveal that ≈6 nm β-CoOOH(01 0), grown on [ 0]-oriented Co, exhibits higher OER activity than ≈3 nm β-CoOOH(10 3) or ≈6 nm β-CoOOH(0006) formed on [02 - and [0001]-oriented Co, respectively. This arises from higher amounts of incorporated hydroxyl ions and more easily reducible CoIII−O sites present in β-CoOOH(01 0) than those in the latter two oxyhydroxide facets. Our correlative multimodal approach shows great promise in linking local activity with atomic-scale details of structure, thickness and composition of active species, which opens opportunities to design pre-catalysts with preferred defects that promote the formation of the most active OER species. 相似文献
4.
Jinghang Shen Thayalan Rajeshkumar Genfeng Feng Yue Zhao Shuao Wang Laurent Maron Congqing Zhu 《Angewandte Chemie (International ed. in English)》2023,62(21):e202303379
Although examples of multiple bonds between actinide elements and main-group elements are quite common, studies of the multiple bonds between actinide elements and transition metals are extremely rare owing to difficulties associated with their synthesis. Here we report the first example of molecular uranium complexes featuring a cis-[M U M] core (M=Rh, Ir), which exhibits an unprecedented arrangement of two M U double dative bond linkages to a single U center. These complexes were prepared by the reactions of chlorine-bridged heterometallic complexes [{U{N(CH3)(CH2CH2NPiPr2)2}(Cl)2[(μ-Cl)M(COD)]2}] (M=Rh, Ir) with MeMgBr or MeLi, a new method for the construction of species with U−M multiple bonds. Theoretical calculations including dispersion confirmed the presence of two U M double dative bonds in these complexes. This study not only enriches the U M multiple bond chemistry, but also provides a new opportunity to explore the bonding of actinide elements. 相似文献
5.
Jinfeng Han Yufeng Jiang Emma Tiernan Connor Ganley Yunjia Song Taein Lee Arlene Chiu Patty McGuiggan Nicholas Adams Paulette Clancy Thomas P Russell Patrick E. Hopkins Susanna M. Thon John D. Tovar Howard E. Katz 《Angewandte Chemie (International ed. in English)》2023,62(23):e202219313
N-Type thermoelectrics typically consist of small molecule dopant+polymer host. Only a few polymer dopant+polymer host systems have been reported, and these have lower thermoelectric parameters. N-type polymers with high crystallinity and order are generally used for high-conductivity ( ) organic conductors. Few n-type polymers with only short-range lamellar stacking for high-conductivity materials have been reported. Here, we describe an n-type short-range lamellar-stacked all-polymer thermoelectric system with highest of 78 S−1, power factor (PF) of 163 μW m−1 K−2, and maximum Figure of merit (ZT) of 0.53 at room temperature with a dopant/host ratio of 75 wt%. The minor effect of polymer dopant on the molecular arrangement of conjugated polymer PDPIN at high ratios, high doping capability, high Seebeck coefficient (S) absolute values relative to , and atypical decreased thermal conductivity ( ) with increased doping ratio contribute to the promising performance. 相似文献
6.
Sandip Chattopadhayay Anupam Ghosh Dr. Titas Kumar Mukhopadhyay Rashmi Sharma Prof. Ayan Datta Prof. Pinaki Talukdar 《Angewandte Chemie (International ed. in English)》2023,62(46):e202313712
The structural tropology and functions of natural cation-anion symporting channels have been continuously investigated due to their crucial role in regulating various physiological functions. To understand the physiological functions of the natural symporter channels, it is vital to develop small-molecule-based biomimicking systems that can provide mechanistic insights into the ion-binding sites and the ion-translocation pathways. Herein, we report a series of bis((R)-(−)-mandelic acid)-linked 3,5-diaminobenzoic acid based self-assembled ion channels with distinctive ion transport ability. Ion transport experiment across the lipid bilayer membrane revealed that compound 1 b exhibits the highest transport activity among the series, and it has interesting selective co-transporting functions, i.e., facilitates K+/ClO4− symport. Electrophysiology experiments confirmed the formation of supramolecular ion channels with an average diameter of 6.2±1 Å and single channel conductance of 57.3±1.9 pS. Selectivity studies of channel 1 b in a bilayer lipid membrane demonstrated a permeability ratio of , , and indicating the higher selectivity of the channel towards KClO4 over KCl salt. A hexameric assembly of a trimeric rosette of 1 b was subjected to molecular dynamics simulations with different salts to understand the supramolecular channel formation and ion selectivity pattern. 相似文献
7.
Ebin Sebastian Mahesh Hariharan 《Angewandte Chemie (International ed. in English)》2023,62(12):e202216482
We report a long-lived charge-separated state in a chromophoric pair ( DC-PDI2 ) that uniquely integrates the advantages of fundamental processes of photosynthetic reaction centers: i) Symmetry-breaking charge-separation (SB-CS) and ii) Marcus-inverted-region dependence. The near-orthogonal bichromophoric DC-PDI2 manifests an ultrafast evolution of the SB-CS state with a time constant of =0.35±0.02 ps and a slow charge recombination (CR) kinetics with =4.09±0.01 ns in ACN. The rate constant of CR of DC-PDI2 is 11 686 times slower than SB-CS in ACN, as the CR of the PDI radical ion-pair occurs in the deep inverted region of the Marcus parabola ( >λ). In contrast, an analogous benzyloxy (BnO)-substituted DC-BPDI2 showcases a ≈10-fold accelerated CR kinetics with lowering to ≈1536 in ACN, by virtue of a decreased CR driving force. The present investigation demonstrates a control of molecular engineering to tune the energetics and kinetics of the SB-CS material, which is essential for next-generation optoelectronic devices. 相似文献
8.
Jin Zhou Shuhe Han Rong Yang Tieliang Li Wenbin Li Dr. Yuting Wang Prof. Yifu Yu Prof. Bin Zhang 《Angewandte Chemie (International ed. in English)》2023,62(27):e202305184
Hydroxylamine (NH2OH), a vital industrial feedstock, is presently synthesized under harsh conditions with serious environmental and energy concerns. Electrocatalytic nitric oxide (NO) reduction is attractive for the production of hydroxylamine under ambient conditions. However, hydroxylamine selectivity is limited by the competitive reaction of ammonia production. Herein, we regulate the adsorption configuration of NO by adjusting the atomic structure of catalysts to control the product selectivity. Co single-atom catalysts show state-of-the-art NH2OH selectivity from NO electroreduction under neutral conditions (FE : 81.3 %), while Co nanoparticles are inclined to generate ammonia (FE : 92.3 %). A series of in situ characterizations and theoretical simulations unveil that linear adsorption of NO on isolated Co sites enables hydroxylamine formation and bridge adsorption of NO on adjacent Co sites induces the production of ammonia. 相似文献
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Sreehari Surendran Rajasree Jierui Yu Dr. H. Christopher Fry Ryther Anderson Dr. Wenqian Xu Riya Krishnan Jiaxin Duan Dr. Subhadip Goswami Prof. Dr. Diego A. Gómez-Gualdrón Prof. Dr. Pravas Deria 《Angewandte Chemie (International ed. in English)》2023,62(38):e202305323
High quantum yield triplets, populated by initially prepared excited singlets, are desired for various energy conversion schemes in solid working compositions like porous MOFs. However, a large disparity in the distribution of the excitonic center of mass, singlet-triplet intersystem crossing (ISC) in such assemblies is inhibited, so much so that a carboxy-coordinated zirconium heavy metal ion cannot effectively facilitate the ISC through spin-orbit coupling. Circumventing this sluggish ISC, singlet fission (SF) is explored as a viable route to generating triplets in solution-stable MOFs. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron super-exchange to generate triplet pairs. Here we show that a predesigned chromophoric linker with extremely poor ISC efficiency (kISC) but form triplets in MOF in contrast to the frameworks that are built from linkers with sizable kISC but . This work opens a new photophysical and photochemical avenue in MOF chemistry and utility in energy conversion schemes. 相似文献
11.
Julia Holz Camilla Pfeffer Hualiang Zuo Dennis Beierlein Gunther Richter Elias Klemm Ren Peters 《Angewandte Chemie (International ed. in English)》2019,58(30):10330-10334
Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional C ?C cross‐coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C ?C bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross‐coupling reaction of an organic halide and an organometallic reagent. 相似文献
12.
Aiping Wang Xiaohong Wu Zheyi Zou Yu Qiao Da Wang Lidan Xing Yuhui Chen Yuxiao Lin Maxim Avdeev Siqi Shi 《Angewandte Chemie (International ed. in English)》2023,62(14):e202217354
LiI and LiBr have been employed as soluble redox mediators (RMs) in electrolytes to address the sluggish oxygen evolution reaction kinetics during charging in aprotic Li-O2 batteries. Compared to LiBr, LiI exhibits a redox potential closer to the theoretical one of discharge products, indicating a higher energy efficiency. However, the reason for the occurrence of solvent deprotonation in LiI-added electrolytes remains unclear. Here, by combining ab initio calculations and experimental validation, we find that it is the nucleophile that triggers the solvent deprotonation and LiOH formation via nucleophilic attack, rather than the increased solvent acidity or the elongated C−H bond as previously suggested. As a comparison, the formation of in LiBr-added electrolytes is found to be thermodynamically unfavorable, explaining the absence of LiOH formation. These findings provide important insight into the solvent deprotonation and pave the way for the practical application of LiI RM in aprotic Li-O2 batteries. 相似文献
13.
Chen Li Yi Pan Tianyu Xiao Luoxing Xiang Dr. Qian Li Dr. Feng Tian Prof. Ian Manners Prof. Yiyong Mai 《Angewandte Chemie (International ed. in English)》2023,62(11):e202215985
We demonstrate a general strategy for the synthesis of ordered bicontinuous-structured metal organic frameworks (MOFs) by using polymer cubosomes (PCs) with a double primitive structure (Im m symmetry) as the template. The filling of MOF precursors in the open channel of PCs, followed by their coordination and removal of the template, generates MOF cubosomes with a single primitive topology (Pm m) and average mesopore diameters of 60–65 nm. Mechanism study reveals that the formation of ZIF-8 cubosomes undergoes a new MOF growth process, which involves the formation of individual MOF seeds in the template, their growth and eventual fusion into the cubosomes. Their growth kinetics follows the Avrami equation with an Avrami exponent of n=3 and a growth rate of k=1.33×10−4, indicating their fast 3D heterogeneous growth mode. Serving as a bioreactor, the ZIF-8 cubosomes show high loading of trypsin enzyme, leading to a high catalytic activity in the proteolysis of bovine serum albumin. 相似文献
14.
Sergey A. Shteingolts Adam I. Stash Vladimir G. Tsirelson Robert R. Fayzullin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(48):e202200985
Intricate behaviour of one-electron potentials from the Euler equation for electron density and corresponding gradient force fields in crystals was studied. Channels of locally enhanced kinetic potential and corresponding saddle Lagrange points were found between chemically bonded atoms. Superposition of electrostatic and kinetic potentials and electron density allowed partitioning any molecules and crystals into atomic - and potential-based -basins; -basins explicitly account for the electron exchange effect, which is missed for -ones. Phenomena of interatomic charge transfer and related electron exchange were explained in terms of space gaps between zero-flux surfaces of - and -basins. The gap between - and -basins represents the charge transfer, while the gap between - and -basins is a real-space manifestation of sharing the transferred electrons caused by the static exchange and kinetic effects as a response against the electron transfer. The regularity describing relative positions of -, -, and - basin boundaries between interacting atoms was proposed. The position of -boundary between - and -ones within an electron occupier atom determines the extent of transferred electron sharing. The stronger an H⋅⋅⋅O hydrogen bond is, the deeper hydrogen atom's -basin penetrates oxygen atom's -basin, while for covalent bonds a -boundary closely approaches a -one indicating almost complete sharing of the transferred electrons. In the case of ionic bonds, the same region corresponds to electron pairing within the -basin of an electron occupier atom. 相似文献
15.
Miao Yan Hai-Ru Li Xin-Xin Tian Yue-Wen Mu Hai-Gang Lu Si-Dian Li 《Journal of computational chemistry》2019,40(11):1227-1232
Detailed molecular orbital and bonding analyses reveal the existence of both fluxional σ- and π-bonds in the global minima Cs ( 1 ) and Cs MB18 ( 3 ) and transition states Cs ( 2 ) and Cs ( 4 ) of dianion and monoanions (M = K, Rb, and Cs). It is the fluxional bonds that facilitate the fluxional behaviors of the quasi-planar and half-sandwich which possess energy barriers smaller than the difference of the corresponding zero-point corrections. © 2019 Wiley Periodicals, Inc. 相似文献
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Dr. Fabian Hecker Lisa Fries Dr. Markus Hiller Prof. Dr. Mario Chiesa Prof. Dr. Marina Bennati 《Angewandte Chemie (International ed. in English)》2023,62(4):e202213700
The hydration structure of nitroxide radicals in aqueous solutions is elucidated by advanced 17O hyperfine (hf) spectroscopy with support of quantum chemical calculations and MD simulations. A piperidine and a pyrrolidine-based nitroxide radical are compared and show clear differences in the preferred directionality of H-bond formation. We demonstrate that these scenarios are best represented in 17O hf spectra, where in-plane coordination over -type H-bonding leads to little spin density transfer on the water oxygen and small hf couplings, whereas -type perpendicular coordination generates much larger hf couplings. Quantitative analysis of the spectra based on MD simulations and DFT predicted hf parameters is consistent with a distribution of close solvating water molecules, in which directionality is influenced by subtle steric effects of the ring and the methyl group substituents. 相似文献
17.
Anbrah E. Alzubidi Prof. Alan M. Bond Assoc. Prof. Lisandra L. Martin 《Chemphyschem》2023,24(20):e202300289
Mechanistic variation in catalysis through substituent-based redox tuning is well established. Fluorination of TCNQ (TCNQ=tetracyanoquinodimethane) provides ~850 mV variation in the redox potentials of the and (n=0, 2, 4) processes. With , catalysis of the kinetically very slow ferrocyanide-thiosulfate redox reaction in aqueous solution occurs via a mechanism in which the catalyst is reduced to when reacting with which is oxidised to . Subsequently, reacts with to form and reform the catalyst, in another thermodynamically favoured process. An analogous mechanism applies with as a catalyst. In contrast, since the reaction of with is thermodynamically unfavourable, an alternative mechanism is required to explain the catalytic activity observed in this non-fluorinated system. Here, upon addition of , reduction of to occurs with concomitant oxidation of to , which then acts as the catalyst for oxidation. Thermodynamic data explain the observed differences in the catalytic mechanisms. (n=0, 4) also act as catalysts for the ferricyanide-thiosulfate reaction in aqueous solution. The present study shows that homogeneous pathways are available following addition of these dissolved materials. Previously, these (n=0, 4) coordination polymers have been regarded as insoluble in water and proposed as heterogeneous catalysts for the ferricyanide-thiosulfate reaction. Details and mechanistic differences were established using UV-visible spectrophotometry and cyclic voltammetry. 相似文献
18.
Peter Glarborg Charlotte S. Andreasen Hamid Hashemi Rachel Qian Paul Marshall 《国际化学动力学杂志》2020,52(12):893-906
A detailed chemical kinetic model for oxidation of methylamine has been developed, based on theoretical work and a critical evaluation of data from the literature. The rate coefficients for the reactions of CHNH + O CHNH / CHNH + HO, CHNH + H CH + NH, CHNH CHNH, and CHNH + O CHNH + HO were calculated from ab initio theory. The mechanism was validated against experimental results from batch reactors, flow reactors, shock tubes, and premixed flames. The model predicts satisfactorily explosion limits for CHNH and its oxidation in a flow reactor. However, oxidation in the presence of nitric oxide, which strongly promotes reaction at lower temperatures, is only described qualitatively. Furthermore, calculated flame speeds are higher than reported experimental values; the model does not capture the inhibiting effect of the NH group in CHNH compared to CH. More work is desirable to confirm the products of the CHNH + NO reaction and to look into possible pathways to NH in methylamine oxidation. 相似文献
19.
Photoabsorption spectra of clusters, N=5–9, have been calculated using a diatomics-in-molecules like electronic structure model and a path-integral Monte Carlo sampling method. A qualitative change in the calculated spectra has been observed at N=9, which has been interpreted in terms of a structural transformation in the clusters consisting in a transition from trimer-like ionic cores observed for N≤7 to dimer-like ionic cores prevailing in through an intermediate state (comparable abundances of both types of ionic cores) observed in . The calculated spectra have been thoroughly compared with an earlier calculation on , , and reported from our group and data available for the same cluster sizes from an experiment. 相似文献
20.
Let be the molecular graph of the linear [n] phenylene with n hexagons and n − 1 squares, and let be the graph obtained by attaching four-membered rings to the terminal hexagons of . In this article, the normalized Laplacian spectrum of consisting of the eigenvalues of two symmetric tridiagonal matrices of order 3n is determined. An explicit closed-form formula of the multiplicative degree-Kirchhoff index (respectively the number of spanning trees) of is derived. Similarly, explicit closed-form formulas of the multiplicative degree-Kirchhoff index and the number of spanning trees of are obtained. It is interesting to see that the multiplicative degree-Kirchhoff index of (respectively ) is approximately to one half of its Gutman index. 相似文献