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991.
992.
Gerui Pei Dr. Pei Zhao Song Xu Xintian Zhao Prof. Chuncai Kong Prof. Zhimao Yang Prof. Masahiro Ehara Prof. Tao Yang 《ChemistryOpen》2020,9(11):1195-1201
The coordination of 10-electron diatomic ligands (BF, CO N2) to iron complexes Fe(CO)2(CNArTripp2)2 [ArTripp2=2,6-(2,4,6-(iso-propyl)3C6H2)2C6H3] have been realized in experiments very recently (Science, 2019 , 363, 1203–1205). Herein, the stability, electronic structures, and bonding properties of (E1E2)Fe-(CO)2(CNArTripp2)2 (E1E2=BF, CO, N2, CN−, NO+) were studied using density functional (DFT) calculations. The ground state of all those molecules is singlet and the calculated geometries are in excellent agreement with the experimental values. The natural bond orbital analysis revealed that Fe is negatively charged while E1 possesses positive charges. By employing the energy decomposition analysis, the bonding nature of the E2E1–Fe(CO)2(CNArTripp2)2 bond was disclosed to be the classic dative bond E2E1→Fe(CO)2(CNArTripp2)2 rather than the electron-sharing double bond. More interestingly, the bonding strength between BF and Fe(CO)2(CNArTripp2)2 is much stronger than that between CO (or N2) and Fe(CO)2(CNArTripp2)2, which is ascribed to the better σ-donation and π back-donations. However, the orbital interactions in CN−→Fe(CO)2(CNArTripp2)2 and NO+→Fe(CO)2(CNArTripp2)2 mainly come from σ-donation and π back-donation, respectively. The different contributions from σ donation and π donation for different ligands can be well explained by using the energy levels of E1E2 and Fe(CO)2(CNArTripp2)2 fragments. 相似文献
993.
Luis K. Ono Shengzhong Liu Yabing Qi 《Angewandte Chemie (International ed. in English)》2020,59(17):6676-6698
In several photovoltaic (PV) technologies, the presence of electronic defects within the semiconductor band gap limit the efficiency, reproducibility, as well as lifetime. Metal halide perovskites (MHPs) have drawn great attention because of their excellent photovoltaic properties that can be achieved even without a very strict film‐growth control processing. Much has been done theoretically in describing the different point defects in MHPs. Herein, we discuss the experimental challenges in thoroughly characterizing the defects in MHPs such as, experimental assignment of the type of defects, defects densities, and the energy positions within the band gap induced by these defects. The second topic of this Review is passivation strategies. Based on a literature survey, the different types of defects that are important to consider and need to be minimized are examined. A complete fundamental understanding of defect nature in MHPs is needed to further improve their optoelectronic functionalities. 相似文献
994.
Jin‐Xia Liang Jian Lin Jingyue Liu Xiaodong Wang Tao Zhang Jun Li 《Angewandte Chemie (International ed. in English)》2020,59(31):12868-12875
Herein, we report a theoretical and experimental study of the water‐gas shift (WGS) reaction on Ir1/FeOx single‐atom catalysts. Water dissociates to OH* on the Ir1 single atom and H* on the first‐neighbour O atom bonded with a Fe site. The adsorbed CO on Ir1 reacts with another adjacent O atom to produce CO2, yielding an oxygen vacancy (Ovac). Then, the formation of H2 becomes feasible due to migration of H from adsorbed OH* toward Ir1 and its subsequent reaction with another H*. The interaction of Ir1 and the second‐neighbouring Fe species demonstrates a new WGS pathway featured by electron transfer at the active site from Fe3+?O???Ir2+?Ovac to Fe2+?Ovac???Ir3+?O with the involvement of Ovac. The redox mechanism for WGS reaction through a dual metal active site (DMAS) is different from the conventional associative mechanism with the formation of formate or carboxyl intermediates. The proposed new reaction mechanism is corroborated by the experimental results with Ir1/FeOx for sequential production of CO2 and H2. 相似文献
995.
Hongyun Ma Hongwu Chen Mingmao Wu Fengyao Chi Feng Liu Jiaxin Bai Huhu Cheng Chun Li Liangti Qu 《Angewandte Chemie (International ed. in English)》2020,59(34):14541-14549
Capacitive energy storage has advantages of high power density, long lifespan, and good safety, but is restricted by low energy density. Inspired by the charge storage mechanism of batteries, a spatial charge density (SCD) maximization strategy is developed to compensate this shortage by densely and neatly packing ionic charges in capacitive materials. A record high SCD (ca. 550 C cm?3) was achieved by balancing the valance and size of charge‐carrier ions and matching the ion sizes with the pore structure of electrode materials, nearly five times higher than those of conventional ones (ca. 120 C cm?3). The maximization of SCD was confirmed by Monte Carlo calculations, molecular dynamics simulations, and in situ electrochemical Raman spectroscopy. A full‐cell supercapacitor was further constructed; it delivers an ultrahigh energy density of 165 Wh L?1 at a power density of 150 WL?1 and retains 120 Wh L?1 even at 36 kW L?1, opening a pathway towards high‐energy‐density capacitive energy storage. 相似文献
996.
Ana Barragn Ane Sarasola Lucia Vitali 《Angewandte Chemie (International ed. in English)》2020,59(36):15599-15602
Efficiency in charge‐transport is a fundamental but demanding prerequisite to allow better exploitation of molecular functionalities in organic electronics and energy‐conversion systems. Here, we report on a mechanism that enables a one‐dimensional conductance structure by connecting discrete molecular states at 2.1 eV through the pores of a metal–organic network on Cu(110). Two adjacent, periodic and isoenergetic contributions, namely a molecular resonance and the confined surface‐state, add‐up leading to anisotropic structures, as channels, observable in real‐space conductance images. The adsorption configurations of Br atoms, inorganic byproduct of the redox‐reacted 4,7‐dibromobenzo[c]‐1,2,5‐thiadiazole (2Br‐BTD) molecules on the copper surface, drive the confinement of the Cu surface state within the pores and critically control the channel continuity. Small displacements of the Br atoms change the local surface potential misaligning the energy levels. This work visualizes the effect of order‐disorder transitions caused by the movement of single atoms in the electronic properties of two‐dimensional organic networks. 相似文献
997.
Felipe L. Oliveira Prof. Dr. Rodrigo B. Capaz Prof. Dr. Pierre M. Esteves 《Chemphyschem》2020,21(1):59-64
A structurally stable microporous metallic carbon allotrope, poly(spiro[2.2]penta-1,4-diyne) or, for short, spiro-carbon, with I41/amd (D4h) symmetry is predicted by first-principles calculations using density functional theory (DFT). The calculations of electronic, vibrational, and structural properties show that spiro-carbon has lower relative energy than other elusive carbon allotropes such as T-Carbon and 1-diamondyne (Y-Carbon). Its structure can be pictured as a set of trans-cisoid-polyacetylene chains tangled and interconnected together by sp3 carbon atoms. Calculations reveal a metallic electronic structure arising from an “intrinsic doping” of trans-cisoid-polyacetylene chains with sp3 carbon atoms. Possible synthetic routes and various simulated spectra (XRD, NMR, and IR absorption) are provided in order to guide future efforts to synthesize this novel material. 相似文献
998.
Kim Eklund Dr. Mikhail S. Kuklin Prof. Dr. Florian Kraus Prof. Antti J. Karttunen 《Chemphyschem》2020,21(8):802-808
Solid gold(I) fluoride remains as an unsynthesized and uncharacterized compound. We have performed a search for potential gold(I) fluoride crystal structures using USPEX evolutionary algorithm and dispersion-corrected hybrid density functional methods. Over 4000 AuF crystal structures have been investigated. Behavior of the AuF crystal structures under pressure was studied up to 25 GPa, and we also evaluated the thermodynamic stability of the hypothetical AuF crystal structures with respect to AuF3, AuF5, and Au3F8. Mixed-valence compound Au3[AuF4] with Au atoms in various formal oxidation states emerged as the thermodynamically most stable AuF species. 相似文献
999.
Dr. Diego Carnevale Marcel Hollenstein Prof. Geoffrey Bodenhausen 《Chemphyschem》2020,21(10):1044-1051
The isotopic enrichment of nucleic acids with nitrogen-15 is often carried out by solid-phase synthesis of oligonucleotides using phosphoramidite precursors that are synthetically demanding and expensive. These synthetic challenges, combined with the overlap of chemical shifts, explain the lag of nitrogen-15 NMR studies of nucleic acids behind those of proteins. For the structural characterization of DNA and RNA-related systems, new NMR methods that exploit the naturally occurring 99.9 % abundant nitrogen-14 isotope are therefore highly desirable. In this study, we have investigated nitrogen-14 spectra of self-assembled quartets based on the nucleobase guanine in the solid state by means of magic-angle spinning NMR spectroscopy. The network of dipolar proton–nitrogen couplings between neighboring stacked purine units is probed by 2D spectra based on 1H→14N→1H double cross-polarization. Interplane dipolar contacts are identified between the stacked G quartets. The assignment is supported by density functional theory (DFT) calculations of the anisotropic chemical shifts and quadrupolar parameters. The experimental spectra are fully consistent with internuclear distances obtained in silico. Averaging of chemical shifts due to internal motions can be interpreted by semiempirical calculations. This method can easily be extended to synthetic G quartets based on nucleobase or nucleoside analogs and potentially to oligonucleotides. 相似文献
1000.
Dr. Carles Acosta-Silva Prof. Joan Bertran Prof. Vicenç Branchadell Prof. Antoni Oliva 《Chemphyschem》2020,21(22):2594-2604
The effect of solvent reaction fields and oriented electric fields on the Kemp elimination reaction between methylamine or imidazole and 5-nitrobenzisoxazole has been theoretically studied. The Kemp reaction is the most widely used for the design of new enzymes. Our results, using the SMD continuous model for solvents, are in quite good agreement with the experimental fact that the rate of the analogous reaction with butylamine is one order of magnitude smaller in water than in acetonitrile. In the case of external electric fields, our results show that they can increase or decrease the energy barrier depending on the magnitude and orientation of the field. A duly oriented electric field may have a notable catalytic effect on the reaction. So, external electric fields and reaction fields due to the medium can contribute to the design of new enzymes. Several factors that must be taken into account to increase the catalytic effect are discussed. 相似文献