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31.
Piotr Matczak 《应用有机金属化学》2019,33(4)
The experimentally well‐known complexation of tin(II) and tin(IV) halides with pyridine (py) leads to structures showing N → Sn coordination. In the present work, the complexes SnXn·mpy (where X = F, Cl, Br, I; n = 2, 4; m = 1, 2) possessing this kind of coordination were studied using a computational quantum chemical approach. Various aspects in the theoretical picture of these complexes were examined to find similarities and differences in their N → Sn coordination. The aspects included, among others, the physical nature of intermolecular interactions, and their role in establishing the structure and energetic stabilization of the complexes. In this context, the effect of tin valency was inspected in great detail. As proven by several theoretical methods, a largely ionic character with a certain covalent component can be attributed to the studied N → Sn coordination, irrespective of tin valency. All complexes are destabilized by py‐py and three‐body interactions, but the Sn(II) complexes experience it to a greater extent. Marked differences are observed in the structural behavior of N → Sn and SnXn during complex formation. This affects the energetics of complexation and, in consequence, the penta‐coordinated Sn(IV) center shows a higher propensity to expand its coordination number, compared with the tri‐coordinated Sn(II) center. The present study supplements the experimental characterization of SnXn·mpy and, in general, it sheds light on the coordination of heteroaromatic nitrogen to tin. The survey of the Cambridge Structural Database revealed that such coordination occurred in a number of crystal structures. 相似文献
32.
《Journal of Coordination Chemistry》2012,65(3):171-180
Abstract 2-(2′-Pyridyl)benzimidazole (pybzim = LH) coordinates to iron(II) as a bidentate and forms the tris-ligated complex, [Fe(pybzim)3]2+ as isolated in the solid. Titration of [Fe(pybzim)3]2+ with base demonstrates the successive deprotonation of the imino hydrogens of the coordinated ligands. Protonation constants for the free ligand, pybzim (Iog10 K H = 11.33) and the complex, [Fe(pybzim)3]2+ (log10 K H 1 = 9.58, log10 K H 2 = 8.13 and log10 K H 3 = 6.97) were measured in 30% (v/v) H2O/EtOH. Results show that coordination to iron(II) increases the acidity of the imino hydrogen of the ligand. Spin-crossover behaviour of the complex were studied in different solvents ME, AC, AN, NM, NB, DMF, DMSO and ANL. The complex shows strong spin-crossover behaviour which is solvent dependent. Values of the spin-equilibrium constant (K sc) and the associated thermodynamic parameters (ΔH sc = 18.1–21.3 kJ mol?1 and δS sc = 69.6–84.4JK?1 mol?1) were calculated. An increase of the enthalpy is observed with increasing donor number (DN) of the solvent. 相似文献
33.
Dr. Shang-Fu Yuan Wen-Di Liu Dr. Chun-Yu Liu Dr. Zong-Jie Guan Prof. Dr. Quan-Ming Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(24):e202104445
Surface organic ligands are critical in dictating the structures and properties of atomically precise metal nanoclusters. In contrast to the conventionally used thiolate, phosphine and alkynyl ligands, nitrogen donor ligands have not been used in the protection for well-defined metal nanoclusters until recently. This review focuses on recent developments in atomically precise metal nanoclusters stabilized by different types of nitrogen donor ligands, in which the synthesis, total structure determination and various properties are covered. We hope that this review will provide insights into the rational design of N donor-protected metal nanoclusters in terms of structural and functional modulation. 相似文献
34.
Rational design of methacrylate monomers containing oxadiazole moieties for single‐layer organic light emitting devices
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Bogdan Zdyrko Yuriy Bandera Volodymyr Tsyalkovsky Christopher F. Huebner Jamie A. Shetzline Parul Rungta Ryan D. Roeder Charles Tonkin Stephen E. Creager Stephen H. Foulger 《Journal of Polymer Science.Polymer Physics》2015,53(23):1663-1673
Methacrylate derived monomers functionalized with pendant oxadiazole moieties were synthesized and copolymerized with carbazole containing monomers to form polymers with electron and hole transporting fragments in the same molecule. Substituents on the oxidazole moiety were varied with the purpose of bandgap tuning and performance optimization when employed in single‐layer organic light emitting devices (OLED). Quantum mechanical calculations of the HOMO‐LUMO levels of the oxidazole derivatives were used to down‐select promising candidates for chemical synthesis and testing in single‐layer OLEDs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1663–1673 相似文献
35.
Sarah R. Geenen Lysander Presser Dr. Torsten Hölzel Prof. Dr. Christian Ganter Prof. Dr. Thomas J. J. Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(36):8064-8075
Differently 5-substituted 8-methoxypsoralens can be synthesized by an efficient synthetic route with various cross-coupling methodologies, such as Suzuki, Sonogashira and Heck reaction. Compared to previously synthesized psoralens, thereby promising daylight absorbing compounds as potentially active agents against certain skin diseases can be readily accessed. Extensive investigations of all synthesized psoralen derivatives reveal fluorescence in the solid state as well as several distinctly emissive derivatives in solution. Donor-substituted psoralens exhibit remarkable photophysical properties, such as high fluorescence quantum yields and pronounced emission solvatochromicity and acidochromicity, which were scrutinized by Lippert–Mataga and Stern–Volmer plots. The results indicate that the compounds exceed the limit of visible light, a significant factor for potential applications as an active agent. In addition, (TD)DFT calculations were performed to elucidate the underlying electronic structure and to assign experimentally obtained data. 相似文献
36.
Dr. Zongrui Wang Dr. Fei Yu Dr. Jian Xie Prof. Jianfeng Zhao Ye Zou Zepeng Wang Prof. Qichun Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(16):3578-3585
Although cocrystallization has provided a promising platform to develop new organic optoelectronic materials, it is still a big challenge to purposely design and achieve specific optoelectronic properties. Herein, a series of mixed-stacking cocrystals (TMFA, TMCA, and TMTQ) were designed and synthesized, and the regulatory effects of the acceptors on the co-assembly behavior, charge-transfer nature, energy-level structures, and optoelectronic characteristics were systematically investigated. The results demonstrate that it is feasible to achieve effective charge-transport tuning and photoresponse switching by carefully regulating the intermolecular charge transfer and energy orbitals. The inherent mechanisms underlying the change in these optoelectronic behaviors were analyzed in depth and elucidated to provide clear guidelines for future development of new optoelectronic materials. In addition, due to the excellent photoresponsive characteristics of TMCA, TMCA-based phototransistors were investigated with varying light wavelength and optical power, and TMCA shows the best performance among all reported cocrystals under UV illumination. 相似文献
37.
Caleb J. Hiller Dr. Chi Chung Lee Dr. Martin T. Stiebritz Lee A. Rettberg Prof. Dr. Yilin Hu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(10):2389-2395
Nitrogenase utilizes an ATP-dependent reductase to deliver electrons to its catalytic component to enable two important reactions: the reduction of N2 to NH4+, and the reduction of CO to hydrocarbons. The two nitrogenase-based reactions parallel the industrial Haber–Bosch and Fischer–Tropsch processes, yet they occur under ambient conditions. As such, understanding the enzymatic mechanism of nitrogenase is crucial for the future development of biomimetic strategies for energy-efficient production of valuable chemical commodities. Mechanistic investigations of nitrogenase has long been hampered by the difficulty to trap substrates and intermediates relevant to the nitrogenase reactions. Recently, we have successfully captured CO on the Azotobacter vinelandii V-nitrogenase via two approaches that alter the electron fluxes in a controlled manner: one approach utilizes an artificial electron donor to trap CO on the catalytic component of V-nitrogenase in the resting state; whereas the other employs a mismatched reductase component to reduce the electron flux through the system and consequently accumulate CO on the catalytic component of V-nitrogenase. Here we summarize the major outcome of these recent studies, which not only clarified the catalytic relevance of the one-CO (lo-CO) and multi-CO (hi-CO) bound states of nitrogenase, but also pointed to a potential competition between N2 and CO for binding to the same pair of reactive Fe sites across the sulfur belt of the cofactor. Together, these results highlight the utility of these strategies in poising the cofactor at a well-defined state for substrate- or intermediate-trapping via controlled alteration of electron fluxes, which could prove beneficial for further elucidation of the mechanistic details of nitrogenase-catalyzed reactions. 相似文献
38.
《Journal of Coordination Chemistry》2012,65(12):2172-2180
A series of Co(II), Ni(II), Cu(II), and Zn(II) complexes of bi- and tridentate hydrazones were prepared. Ligands L1 and L2 were synthesized by the condensation of 2-mercapto-3-hydrazinoquinoxaline with 2-hydroxy-3-formylquinoline and 3-acetylcoumarin, respectively. The compounds were characterized by various spectro-analytical techniques and magnetic moment studies. The complexes are found to be monomeric and non-electrolytes. In these complexes, [CuL1Cl2] has square pyramidal geometry and others have octahedral. The copper complexes are electrochemically active in the applied potential range. 相似文献
39.
Stephen Brand John Milton Martin F. Jones Christopher M. Rayner 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):367-368
A new method for the synthesis of cyclic and acyclic optically active S,O-acetals is reported, along with subsequent stereocontrolled transformations, culminating in a synthesis of the important antiviral nucleoside Lamivudine. 相似文献
40.
The amination reactions of chloromethylated polystyrene with N,N-dimethyldodecylamine, N,N-dimethyltetradecylamine, and N,N-dimethylhexadecylamine were studied. The physical properties, particularly the solubility properties of the resulting polymers, are influenced by the hydrophobic properties of the long alkyl chain on the N+ atoms. The main factor that influences the kinetics of the reactions is the polymersolvent interaction parameter. 相似文献