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41.
Stabilization of the Low‐Spin State in a Mononuclear Iron(II) Complex and High‐Temperature Cooperative Spin Crossover Mediated by Hydrogen Bonding
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Dr. Sipeng Zheng Niels R. M. Reintjens Dr. Maxime A. Siegler Dr. Olivier Roubeau Prof. Elisabeth Bouwman Andrii Rudavskyi Prof. Remco W. A. Havenith Dr. Sylvestre Bonnet 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(1):331-339
The tetrapyridyl ligand bbpya (bbpya=N,N‐bis(2,2′‐bipyrid‐6‐yl)amine) and its mononuclear coordination compound [Fe(bbpya)(NCS)2] ( 1 ) were prepared. According to magnetic susceptibility, differential scanning calorimetry fitted to Sorai’s domain model, and powder X‐ray diffraction measurements, 1 is low‐spin at room temperature, and it exhibits spin crossover (SCO) at an exceptionally high transition temperature of T1/2=418 K. Although the SCO of compound 1 spans a temperature range of more than 150 K, it is characterized by a wide (21 K) and dissymmetric hysteresis cycle, which suggests cooperativity. The crystal structure of the LS phase of compound 1 shows strong N?H???S intermolecular H‐bonding interactions that explain, at least in part, the cooperative SCO behavior observed for complex 1 . DFT and CASPT2 calculations under vacuum demonstrate that the bbpya ligand generates a stronger ligand field around the iron(II) core than its analogue bapbpy (N,N′‐di(pyrid‐2‐yl)‐2,2′‐bipyridine‐6,6′‐diamine); this stabilizes the LS state and destabilizes the HS state in 1 compared with [Fe(bapbpy)(NCS)2] ( 2 ). Periodic DFT calculations suggest that crystal‐packing effects are significant for compound 2 , in which they destabilize the HS state by about 1500 cm?1. The much lower transition temperature found for the SCO of 2 compared to 1 appears to be due to the combined effects of the different ligand field strengths and crystal packing. 相似文献
42.
Ivachtchenko AV Kobak VV Ilyn AP Khvat AV Kysil VM Williams CT Kuzovkova JA Kravchenko DV 《Journal of combinatorial chemistry》2005,7(2):227-235
Two efficient strategies for solution-phase parallel synthesis of libraries of quinoline derivatives are described. The first synthetic pathway features the Pfitzinger reaction of isatin with diethyl malonate and sulfochlorination of the resulting 2-oxo-1,2-dihydroquinoline-4-carboxylate followed by generation of sulfonamide library. The second strategy employs the unusual behavior of 5-sulfamoylisatins in Pfitzinger reactions, which results in formation of 6-sulfamoyl-4-carboxyquinolines instead of the anticipated 2-oxo-1,2-dihydroquinoline structures. The obtained carboxylates appeared to be convenient synthetic intermediates for the generation of the corresponding carboxamide libraries. Using these reagents, the parallel solution-phase synthesis of more than 500 substituted quinoline and 2-oxo-1,2-dihydroquinoline derivatives has been accomplished on the 50-100-mg scale. Simple manual techniques for parallel reactions using special CombiSyn synthesizers were coupled with easy purification procedures to give high-purity final products. The scope and limitations of the developed approaches are discussed. 相似文献
43.
N-Substituted 5-piperazin-1-yl-1,3,4-thiadiazol-2-amines that fail to undergo Groebke-Blackburn type MCR with aldehydes and isocyanides provide fair to good yields of the respective 2-piperazin-1-ylimidazo[2,1-b][1,3,4]thiadiazoles when such reaction is promoted by an equimolar quantity of trimethylsilyl chloride in aprotic medium. These findings further extend the utility of TMSCl as the isocyanide-based MCR promoter, and also demonstrate that this silicon Lewis acid is the actual promoter of the reaction. 相似文献
44.
Abdoul Aziz Ndiaye Ana Lacoste Alexandre Bès Andrii Zaitsev Fabienne Poncin-Epaillard Dominique Debarnot 《Plasma Chemistry and Plasma Processing》2018,38(4):887-902
In the wavelength range from 200 up to 1000 nm, optical emission from electronically excited fragments (CN, CH, NH, C2, H2, N2, N2+, and H-Balmer) is detected when aniline plasmas are generated in a multi-dipolar microwave reactor. The optical emission spectrum monitored in very low-pressure conditions (~?1 mTorr) shows important characteristics. The Hα, Hβ and CN species are the most radiating systems and according to the NH/N2 intensity ratio, two different operating regimes are observed suggesting a change in the reaction pathways. These two regimes are correlated to changes of the plasma characteristics (electron temperature and density) deduced from Langmuir probe measurements. The plasma thermodynamic state is quantified by implementing numerical simulation codes for synthetic spectra calculations. The rovibrational temperatures (Tr, Tv) are determined for some neutral species (CN, CH). The obtained values of Tr and Tv show the non-local thermodynamic equilibrium of the vibrational and rotational states (Tr?<?Tv). Moreover, the very low pressure aniline-based plasmas deviate substantially from the Boltzmann distribution. Correlation between the optical emission data and the solid phase analysis allows proving that the in situ characterization of the plasma phase is an important predictive tool of physico-chemical properties of the film. From these correlated data, we deduce preponderant chemical reaction pathways which help to better understand the plasma generation. Relative contributions of the dehydrogenation of C–H and N–H groups are established in order to deduce the leading initiation reaction for H-Balmer line formation. 相似文献
45.
Nikolay Gromov Vladimir Kazakov Andrii Kozak Pedro Vieira 《Letters in Mathematical Physics》2010,91(3):265-287
Using the thermodynamic Bethe ansatz method we derive an infinite set of integral non-linear equations for the spectrum of
states/operators in AdS/CFT. The Y-system conjectured in Gromov et al. (Integrability for the Full Spectrum of Planar AdS/CFT. arXiv:0901.3753 [hep-th]) for
the spectrum of all operators in planar N = 4 SYM theory follows from these equations. In particular, we present the integral TBA type equations for the spectrum of
all operators within the sl(2) sector. We prove that all the kernels and free terms entering these TBA equations are real and have nice fusion properties
in the relevant mirror kinematics. We find the analog of DHM formula for the dressing kernel in the mirror kinematics. 相似文献
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47.
Igor Sharf Andrii Tykhonov Grygorii Sokhrannyi Maksym Deliyergiyev Natalia Podolyan Vitaliy Rusov 《Central European Journal of Physics》2012,10(4):858-887
We demonstrate a new method to calculate inelastic scattering cross-sections, which in contrary to the Regge-based methods takes into account the energy momentum conservation law. It is shown that the main contribution to integral expressing inelastic scattering cross-sections does not come from the multi-Regge domain. In particular, accounting for the longitudinal momenta contribution to virtualities is sufficient and results in the new mechanism of cross-section growth. The reasons for taking into account the sufficiently high number of interference contributions are shown and the approximate method for this purpose is developed. By fitting single free parameter of the model achieved a qualitative agreement of the total and inelastic cross sections with experimental data. 相似文献
48.
Petro P. Onys’ko Denys V. Klukovsky Andrii V. Bezdudny Volodymyr V. Pirozhenko Yurii M. Pustovit Anatoly D. Synytsya 《Phosphorus, sulfur, and silicon and the related elements》2014,189(7-8):1094-1101
AbstractA convenient synthetic approach for previously unknown N-(R-cyclopropyl)trifluoroacetimidoyl phosphonates 5a,b (R?H, CF3) was developed on the basis of the reaction of respective trifluoroacetimidoyl chlorides with triethyl phosphite. It was shown that imidoyl phosphonates 5a,b exist as equilibrium mixture of Z/E isomers (Z:E ~92:8). Activation parameters of Z–E isomerization were evaluated by 19F NMR spectroscopy. Catalytic hydrogenation of 5a,b can serve as a convenient method for the synthesis of trifluoroethylaminophosphonates with a rigid N-cyclopropyl group. 相似文献
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We show that the existence of a non-coercive Lyapunov function is sufficient for uniform global asymptotic stability (UGAS) of infinite-dimensional systems with external disturbances provided the speed of decay is measured in terms of the norm of the state and an additional mild assumption is satisfied. For evolution equations in Banach spaces with Lipschitz continuous nonlinearities these additional assumptions become especially simple. The results encompass some recent results on linear switched systems on Banach spaces. Finally, we derive new non-coercive converse Lyapunov theorems and give some examples showing the necessity of our assumptions. 相似文献