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51.
52.
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
53.
Simultaneous Aromatic–Beryllium Bonds and Aromatic–Anion Interactions: Naphthalene and Pyrene as Models of Fullerenes,Carbon Single‐Walled Nanotubes,and Graphene 下载免费PDF全文
Dr. Marta Marín‐Luna Prof. Ibon Alkorta Prof. José Elguero Prof. Otilia Mó Prof. Manuel Yáñez 《Chemphyschem》2015,16(12):2680-2686
The possibility of forming stable BeR2:ArH:Y? (R=H, F, Cl; ArH=naphthalene, pyrene; Y=Cl, Br) ternary complexes in which the beryllium compounds and anions are located on the opposite sides of an extended aromatic system is explored by means of MP2/aug‐cc‐pVDZ ab initio calculations. Comparison of the electron‐density distribution of these ternary complexes with the corresponding BeR2:ArH and ArH:Y? binary complexes reveals the existence of significant cooperativity between the two noncovalent interactions in the triads. The energetic effects of this cooperativity are quantified by evaluation of the three‐body interaction energy Δ3E in the framework of the many‐body interaction‐energy (MBIE) approach. Although an essential component of the interaction energies is electrostatic and is well reflected in the changes in the molecular electrostatic potential of the aromatic system on complexation, strong polarization effects, in particular for the BeR2:ArH interactions, also play a significant role. The charge transfers associated with these polarization effects are responsible for significant distortion of both the BeR2 and the aromatic moieties. The former are systematically bent in all the complexes, and the latter are curved to a degree that depends on the nature of the R substituents of the BeR2 subunit. 相似文献
54.
Computational Study of Proton Transfer in Tautomers of 3‐ and 5‐Hydroxypyrazole Assisted by Water 下载免费PDF全文
Dr. Cristina Trujillo Dr. Goar Sánchez‐Sanz Prof. Ibon Alkorta Prof. José Elguero 《Chemphyschem》2015,16(10):2140-2150
The tautomerism of 3‐ and 5‐hydroxypyrazole is studied at the B3LYP, CCSD and G3B3 computational levels, including the gas phase, PCM–water effects, and proton transfer assisted by water molecules. To understand the propensity of tautomerization, hydrogen‐bond acidity and basicity of neutral species is approached by means of correlations between donor/acceptor ability and H‐bond interaction energies. Tautomerism processes are highly dependent on the solvent environment, and a significant reduction of the transition barriers upon solvation is seen. In addition, the inclusion of a single water molecule to assist proton transfer decreases the barriers between tautomers. Although the second water molecule further reduces those barriers, its effect is less appreciable than the first one. Neutral species present more stable minima than anionic and cationic species, but relatively similar transition barriers to anionic tautomers. 相似文献
55.
UV Emission of Gd3+ in the Presence of Cu2+: Towards Luminescence Quenching through Quantum Cutting? 下载免费PDF全文
Dr. José A. Jiménez 《Chemphyschem》2015,16(8):1683-1686
The first investigation into the ultraviolet (UV) photoluminescence of gadolinium(III) in the presence of copper(II) is reported. A melt‐quenched barium phosphate glass was used as a model matrix. The optical spectroscopy assessment shows that with increasing CuO concentration the Cu2+ absorption band grows steadily, whereas the UV emission from Gd3+ ions is progressively quenched. The data, thus, suggests the existence of a Gd3+→Cu2+ energy‐transfer process ocurring through quantum cutting. A downconversion/cross‐relaxation pathway proceeding through a virtual state in Gd3+ is proposed. These findings suggest gadolinium(III) could potentially be used in the optical sensing of copper(II). 相似文献
56.
Supercritical fluid chromatography with photodiode array detection for pesticide analysis in papaya and avocado samples 下载免费PDF全文
Norma S. Pano‐Farias Silvia G. Ceballos‐Magaña Jorge Gonzalez José M. Jurado Roberto Muñiz‐Valencia 《Journal of separation science》2015,38(7):1240-1247
To improve the analysis of pesticides in complex food matrices with economic importance, alternative chromatographic techniques, such as supercritical fluid chromatography, can be used. Supercritical fluid chromatography has barely been applied for pesticide analysis in food matrices. In this paper, an analytical method using supercritical fluid chromatography coupled to a photodiode array detection has been established for the first time for the quantification of pesticides in papaya and avocado. The extraction of methyl parathion, atrazine, ametryn, carbofuran, and carbaryl was performed through the quick, easy, cheap, effective, rugged, and safe methodology. The method was validated using papaya and avocado samples. For papaya, the correlation coefficient values were higher than 0.99; limits of detection and quantification ranged from 130–380 and 220–640 μg/kg, respectively; recovery values ranged from 72.8–94.6%; precision was lower than 3%. For avocado, limit of detection values were ?450 μg/kg; precision was lower than 11%; recoveries ranged from 50.0–94.2%. Method feasibility was tested for lime, banana, mango, and melon samples. Our results demonstrate that the proposed method is applicable to methyl parathion, atrazine, ametryn, and carbaryl, toxics pesticides used worldwide. The methodology presented in this work could be applicable to other fruits. 相似文献
57.
Tingting Zhang Wanying Lei Ping Liu José A. Rodriguez Jiaguo Yu Yang Qi Gang Liu Minghua Liu 《Chemical science》2015,6(7):4118-4123
Structure–function correlations are a central theme in heterogeneous (photo)catalysis. In this study, the geometric and electronic structure of perovskite ferroelectric KNbO3 nanowires with respective orthorhombic and monoclinic polymorphs have been systematically addressed. By virtue of aberration-corrected scanning transmission electron microscopy, we directly visualize surface photocatalytic active sites, measure local atomic displacements at an accuracy of several picometers, and quantify ferroelectric polarization combined with first-principles calculations. The photoreactivity of the as-prepared KNbO3 nanowires is assessed toward aqueous rhodamine B degradation under UV light. A synergy between the ferroelectric polarization and electronic structure in photoreactivity enhancement is uncovered, which accounts for the prominent reactivity order: orthorhombic > monoclinic. Additionally, by identifying new photocatalytic products, rhodamine B degradation pathways involving N-deethylation and conjugated structure cleavage are proposed. Our findings not only provide new insights into the structure–photoreactivity relationships in perovskite ferroelectric photocatalysts, but also have broad implications in perovskite-based water splitting and photovoltaics, among others. 相似文献
58.
The first nickel catalyzed deprotonative cross coupling between C(sp3)–H bonds and aryl chlorides is reported, allowing the challenging arylation of benzylimines in the absence of directing group or stoichiometric metal activation. This methodology represents a convenient access to the (diarylmethyl)amine moiety, which is widespread in pharmaceutically relevant compounds. 相似文献
59.
Juan Carlos Pardo José-Luis Pérez Victor Pérez-Abreu 《Journal of Functional Analysis》2017,272(1):339-362
We investigate the process of eigenvalues of a fractional Wishart process defined by , where B is the matrix fractional Brownian motion recently studied in [18]. Using stochastic calculus with respect to the Young integral we show that, with probability one, the eigenvalues do not collide at any time. When the matrix process B has entries given by independent fractional Brownian motions with Hurst parameter , we derive a stochastic differential equation in the Malliavin calculus sense for the eigenvalues of the corresponding fractional Wishart process. Finally, a functional limit theorem for the empirical measure-valued process of eigenvalues of a fractional Wishart process is obtained. The limit is characterized and referred to as the non-commutative fractional Wishart process, which constitutes the family of fractional dilations of the free Poisson distribution. 相似文献
60.
We solve the isomorphism problem in the context of abstract algebraic logic and of π-institutions, namely the problem of when the notions of syntactic and semantic equivalence among logics coincide. The problem is solved in the general setting of categories of modules over quantaloids. We introduce closure operators on modules over quantaloids and their associated morphisms. We show that, up to isomorphism, epis are morphisms associated with closure operators. The notions of (semi-)interpretability and (semi-)representability are introduced and studied. We introduce cyclic modules, and provide a characterization for cyclic projective modules as those having a g-variable. Finally, we explain how every π-institution induces a module over a quantaloid, and thus the theory of modules over quantaloids can be considered as an abstraction of the theory of π-institutions. 相似文献