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排序方式: 共有1028条查询结果,搜索用时 343 毫秒
1.
Electronic Structure Modulation in an Exceptionally Stable Non‐Heme Nitrosyl Iron(II) Spin‐Crossover Complex 下载免费PDF全文
Lucía Piñeiro‐López Dr. Norma Ortega‐Villar Prof. Dr. M. Carmen Muñoz Dr. Gábor Molnár Dr. Jordi Cirera Prof. Dr. Rafael Moreno‐Esparza Prof. Dr. Víctor M. Ugalde‐Saldívar Dr. Azzedine Bousseksou Prof. Dr. Eliseo Ruiz Prof. Dr. José A. Real 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(36):12741-12751
The highly stable nitrosyl iron(II) mononuclear complex [Fe(bztpen)(NO)](PF6)2 (bztpen=N‐benzyl‐N,N′,N′‐tris(2‐pyridylmethyl)ethylenediamine) displays an S=1/2?S=3/2 spin crossover (SCO) behavior (T1/2=370 K, ΔH=12.48 kJ mol?1, ΔS=33 J K?1 mol?1) stemming from strong magnetic coupling between the NO radical (S=1/2) and thermally interconverted (S=0?S=2) ferrous spin states. The crystal structure of this robust complex has been investigated in the temperature range 120–420 K affording a detailed picture of how the electronic distribution of the t2g–eg orbitals modulates the structure of the {FeNO}7 bond, providing valuable magneto–structural and spectroscopic correlations and DFT analysis. 相似文献
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Formation of Long,Multicenter π‐[TCNE]22− Dimers in Solution: Solvation and Stability Assessed through Molecular Dynamics Simulations
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Dr. Marçal Capdevila‐Cortada Dr. Jordi Ribas‐Arino Dr. Alain Chaumont Prof. Georges Wipff Prof. Juan J. Novoa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):17037-17046
Purely organic radical ions dimerize in solution at low temperature, forming long, multicenter bonds, despite the metastability of the isolated dimers. Here, we present the first computational study of these π‐dimers in solution, with explicit consideration of solvent molecules and finite temperature effects. By means of force‐field and ab initio molecular dynamics and free energy simulations, the structure and stability of π‐[TCNE]22? (TCNE=tetracyanoethylene) dimers in dichloromethane have been evaluated. Although the dimers dissociate at room temperature, they are stable at 175 K and their structure is similar to the one in the solid state, with a cofacial arrangement of the radicals at an interplanar separation of approximately 3.0 Å. The π‐[TCNE]22? dimers form dissociated ion pairs with the NBu4+ counterions, and their first solvation shell comprises approximately 20 CH2Cl2 molecules. Among them, the eight molecules distributed along the equatorial plane of the dimer play a key role in stabilizing the dimer through bridging C?H???N contacts. The calculated free energy of dimerization of TCNE . ? in solution at 175 K is ?5.5 kcal mol?1. These results provide the first quantitative model describing the pairing of radical ions in solution, and demonstrate the key role of solvation forces on the dimerization process. 相似文献
4.
Pau Turon Prof. Dr. Jordi Puiggalí Dr. Oscar Bertrán Prof. Dr. Carlos Alemán 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(52):18892-18898
Even in the worst of conditions, such as those which occurred during mass extinction events, life on Earth never totally stopped. Aggressive chemical and physical attacks able to sterilize or poison living organisms occurred repeatedly. Surprisingly, DNA was not degraded, denatured or modified to the point of losing the capability of transferring the genetic information to the next generations. After the events of mass extinction life was able to survive and thrive. DNA was passed on despite being an extremely fragile biomolecule. The potential implications of hydroxyapatite protection of DNA are discussed in this Concept article including how DNA acts as a template for hydroxyapatite (HAp) formation, how cell death can trigger biomineralization, and how DNA can be successfully released from HAp when the conditions are favorable for life. 相似文献
5.
Dr. Anton Lishchynskyi Dr. Fedor M. Miloserdov Dr. Eddy Martin Dr. Jordi Benet‐Buchholz Eduardo C. Escudero‐Adán Dr. Andrey I. Konovalov Dr. Vladimir V. Grushin 《Angewandte Chemie (International ed. in English)》2015,54(50):15289-15293
First evidence for the existence of free trifluoromethyl anion CF3? has been obtained. The 3D‐caged potassium cation in [K(crypt‐222)]+ is inaccessible to CF3?, thus rendering it uncoordinated (“naked”). Ionic [K(crypt‐222)]+ CF3? has been characterized by single‐crystal X‐ray diffraction, solution NMR spectroscopy, DFT calculations, and reactivity toward electrophiles. 相似文献
6.
Eva Blokker Dr. Xiaobo Sun Prof. Dr. Jordi Poater Dr. Ir. J. Martijn van der Schuur Dr. Trevor A. Hamlin Prof. Dr. F. Matthias Bickelhaupt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(63):15616-15622
We have quantum chemically analyzed element−element bonds of archetypal HnX−YHn molecules (X, Y=C, N, O, F, Si, P, S, Cl, Br, I), using density functional theory. One purpose is to obtain a set of consistent homolytic bond dissociation energies (BDE) for establishing accurate trends across the periodic table. The main objective is to elucidate the underlying physical factors behind these chemical bonding trends. On one hand, we confirm that, along a period (e. g., from C−C to C−F), bonds strengthen because the electronegativity difference across the bond increases. But, down a period, our findings constitute a paradigm shift. From C−F to C−I, for example, bonds do become weaker, however, not because of the decreasing electronegativity difference. Instead, we show that the effective atom size (via steric Pauli repulsion) is the causal factor behind bond weakening in this series, and behind the weakening in orbital interactions at the equilibrium distance. We discuss the actual bonding mechanism and the importance of analyzing this mechanism as a function of the bond distance. 相似文献
7.
Jordi Castro Stefano Nasini Francisco Saldanha-da-Gama 《Mathematical Programming》2017,163(1-2):411-444
We propose a cutting-plane approach (namely, Benders decomposition) for a class of capacitated multi-period facility location problems. The novelty of this approach lies on the use of a specialized interior-point method for solving the Benders subproblems. The primal block-angular structure of the resulting linear optimization problems is exploited by the interior-point method, allowing the (either exact or inexact) efficient solution of large instances. The consequences of different modeling conditions and problem specifications on the computational performance are also investigated both theoretically and empirically, providing a deeper understanding of the significant factors influencing the overall efficiency of the cutting-plane method. The methodology proposed allowed the solution of instances of up to 200 potential locations, one million customers and three periods, resulting in mixed integer linear optimization problems of up to 600 binary and 600 millions of continuous variables. Those problems were solved by the specialized approach in less than one hour and a half, outperforming other state-of-the-art methods, which exhausted the (144 GB of) available memory in the largest instances. 相似文献
8.
Michele Tomasini Dr. Lucia Caporaso Jonathan Trouvé Dr. Jordi Poater Dr. Rafael Gramage-Doria Dr. Albert Poater 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(57):e202201970
Non-biological catalysts following the governing principles of enzymes are attractive systems to disclose unprecedented reactivities. Most of those existing catalysts feature an adaptable molecular recognition site for substrate binding that are prone to undergo conformational selection pathways. Herein, we present a non-biological catalyst that is able to bind substrates via the induced fit model according to in-depth computational calculations. The system, which is constituted by an inflexible substrate-recognition site derived from a zinc-porphyrin in the second coordination sphere, features destabilization of ground states as well as stabilization of transition states for the relevant iridium-catalyzed C−H bond borylation of pyridine. In addition, this catalyst appears to be most suited to tightly bind the transition state rather than the substrate. Besides these features, which are reminiscent of the action modes of enzymes, new elementary catalytic steps (i. e. C−B bond formation and catalyst regeneration) have been disclosed owing to the unique distortions encountered in the different intermediates and transition states. 相似文献
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10.
The exchange of chemical species between the atmospheric boundary layer and the reservoir layer is investigated by means of an analytical solution of the conservation equation of a decaying chemical species. The exchange mechanism is governed by two parameters: the Damköhler number (the ratio of the turbulence time scale to the chemical time scale) and the ratio of a concentration scale in the atmospheric boundary layer to the concentration in the reservoir layer. Depending on the value of these two parameters, the exchange flux between the two layers can vary in sign and by several orders of magnitude. The study demonstrates to what extent chemical transformation determines the transfer of chemical species between the atmospheric boundary layer and the reservoir layer. 相似文献