Ionic iron（III） complex of aryloxo-linked bis（imidazolium） cations： efficient and recyclable catalyst for aryl Grignard cross-coupling of alkyl chlorides

A novel phenol-linked bis（imidazolium） salt, H3LCl2 （L = O-4-C（CH3）3-C6H2-2,6-di[CH2{C（NCHCH- NAr）}]2, Ar = 2,6-diisopropylphenyl, 1）, was designed and used to prepare an ionic iron（III） complex [H2L][FeCl4] （2）. Complex 2 was a highly efficient catalyst for aryl Grignard cross-coupling of alkyl chlorides bearing β-hydrogens. Furthermore, complex 2 was reusable and could be reused in at least eight times without significant loss in catalytic activity.     

Well-defined bis（phenolate） lanthanide methoxides as efficient initiators for the polymerization of cyclic carbonate and lactide

Lanthanide methoxides supported by carbon-bridged bis(phenolate) ligands 2,2′-methylene-bis(6-tert- butyl-4-methylphenoxo) (MBMP2-) [(MBMP)Ln( μ-OMe)(THF)2]2 (Ln = Nd (1), Yb (2)) were synthesized in high yields by the protolysis reaction using (C5H5)3Ln(THF) as starting materials, and complex 1 was structurally characterized. The coordination geometry around the center metal can be best described as a distorted octahedron. Complexes 1 and 2 were shown to be efficient initiators for the ring-opening polymerization of 2,2-dimethyltrimethylene carbonate (DTC) and L-lactide. The mechanism of DTC polymerization was explored by the end group analysis of the oligomer.     

Synthesis, structure, optoelectronic properties of novel zinc Schiff-base complexes

Two novel zinc Schiff-base complexes, bis-(N-(2-hydroxybenzidene)-p-aminodimethylaniline)zinc(II) (2) and bis-(N-(2-hydroxy-1-naphthidene)-p-aminodimethylaniline)zinc(II) (4) were designed and synthesized. Both the complexes exhibit good solubility in organic solvents and excellent thermal stabilities. A single crystal of 2 was grown and its crystalline structure was determined from X-ray diffraction data. Analysis of the electronic structures of both the zinc complexes calculated by density functional theory reveals a localization of orbital. The UV-Vis absorption and photoluminescence profiles of 4 in thin film are similar to those of 2, but the emission for 4 is red-shifted compared to 2. Three-layered devices with a configuration of ITO/NPB/2/Alq 3 /LiF/Al and ITO/NPB/4/Alq 3 /LiF/Al show a yellow and red emission, respectively.     

Synthesis, structure of iron(III)-containing imidazolium salts and their catalytic activity in the alkylation of aryl Grignard reagents

A series of iron(III)-containing imidazolium salts of the general formula [DRim][FeX₄] (R = 2,6-diisopropylphenyl, IPr, X = Cl, 1; R = IPr, X = Br, 2; R = tertbutyl, ^t Bu, X = Cl, 3; R = isopropyl, ⁱ Pr, X = Cl, 4; R = benzyl, Bn, X = Cl, 5; R = Bn, X = Br, 6) have been prepared in high yields via reactions of anhydrous ferric halides with equivalent of the corresponding N,N-dihydrocarby-limidazolium halides, where 2–6 are novel ones. All of the complexes were characterized by elemental analysis, Raman spectroscopy, electrospray ionization mass spectroscopy, and X-ray crystallography for 1 and 2. All of them were non-hygroscopic and air-stable, with four of them existing as solids (1–4) and two as liquids (5 and 6) at room temperature. A preliminary catalytic study on the coupling of 4-tolylmagnesium bromide with cyclohexyl bromide revealed that 1 and 3 possessed the highest activity. In comparison, 2, 4 and 5 exhibited moderate activity and the least active complex was 6.     

4-Formyl-2-（2H-benzotriazol-2-yl）-phenol： an ESIPT chromophore

In the present work, excited state intramolecular proton transfer （ESIPT） emission properties of a new benzotriazole derivative 4-formyl-2-（2H-benzotriazol-2-yl）- phenol （C1） were studied. 4-Formyl-2-（2H-benzotriazol-2- yl）-methoxy-benzene （C2）, 4-formyl-2-（2H-benzotriazol-2- yl）-phenyl acetate （C3） and 4-methyl-2-（2H-benzotriazol- 2-yl）-phenol （C4） were used as the reference molecules. ^1H NMR chemical shift of hydroxy group in C1 was located at more down field than that of C4 or p-hydroxy-benzaldehyde （C5）, respectively. C1 showed two absorption bands in the range of 260-400 nm zones in various solvents, while C2 and C3 exhibited single absorption band. The equal molar mixtures of C2/C5 or C3/C5 showed single absorption band. C2 and C3 displayed single fluorescence emission band in various solvents, while C1 exhibited dual emission bands in some strong polar solvents. Furthermore, the second emission band in these strong polar solvents showed the large Stokes shift. The results show that the second emission band of C1 was produced by ESIPT. C2 and C3 could not undergo ESIPT due to no hydroxy group. The geometry optimization calculation of enol and keto forms in the ground and excited states of C1 provided tough theoretical evidences of ESIPT.     

Development of Fe(III)-containing ether-functionalized imidazolium ionic liquids for aryl Grignard cross-coupling of alkyl halides

A series of Fe(Ⅲ)-containing imidazolium-based ionic liquids containing ether substituents,including[C3OMim][FeCl4](1,[C3OMim]=1-(2-methoxyethyl)-3-methylimidazolium),[C3OiPim][FeCl4](2,[C3OiPim]=1-isopropyl-3-(2-methoxyethyl)imidazolium),[C3OBim][FeCl4](3,[C3OBim]=1-butyl-3-(2-methoxyethyl)imidazolium),[(C3O)2im][FeCl4](4,[(C3O)2im]=1,3-bis(2-methoxyethyl)imidazolium),[C3OMim][FeBr4](5)and[(C3O)2im][FeBr4](6),were prepared and characterized by elemental analysis,Raman spectroscopy and electrospray ionization mass spectrometry.The catalytic performances of 1–6 and related Fe(III)-based catalysts in the cross-coupling of aryl Grignard reagents with alkyl halides bearing-hydrogens were studied,revealing that mono(ether)functionality improves the catalytic activity and that bis(ether)functionality improves the reusability.After simply decanting the product contained in the ethereal layer,complex 4,which containing bis(ether)-functionalized imidazolium cation,could be successfully recycled seven times.     

New terpenoids from the roots of Jatropha curcas

Two new sesquiterpenoids,(1S,2R)-dihydroxycycloax-4(15)-ene(1),14-dehydroxyl daucucarotol(2),and one new rhamnofalane diterpenoid,2-hydroxy-3-dehydroxycaniojane(3),together with two known compounds,curcusone D(4) and curcusone C(5),were isolated from the roots of Jatropha curcas.The chemical structures of these compounds were established by chemical methods and extensive 1D-and 2D-NMR spectroscopic data analyses.     

An operator on ascent sequences

We solve two problems about ascent sequences: how to get the ascent sequence of the reflection of A with respect to its antidiagonal for a matrix A∈ Intn and its ascent sequences, and how to determine the ascent sequence of A+B for k×k matrices A∈ Intn and B∈ Intm. We give the other definition of ascent sequence and get M-sequence. For the first question, we define M-sequence of A and rewrite the ascent sequences as another form.We build the bijection between M-sequences and ascent sequences and prove that our bijection is well-defined. For the second question, we define an operation on M-sequences. On the basis of the operation and the bijections, we get the ascent sequences of the sum of two matrices.     

Synthesis, spectra, structure and quantum chemistry study on two novel oxovanadium complexes with hydrotris （pyrazolyl） borate ligands

Vanadium is a trace element in lives. Though vana- dium was investigated in life science from 1876, the importance of vanadium in lives was not recognized until 1971[1,2]. Since bromoperoxidase and nitrogenase were found and proved that vanadium plays an …     

Synthesis and self-assembly of two 1,3-alternate thiacalix[4]arenes derivatives bearing amide groups

Two 1,3-alternate thiacalix[4]arene derivatives bearing amide groups, 1,3-alternate p-tert-butylthiacalix[4]arene tetraamide (4), and 1,3-alternate p-H-thiacalix[4]arene tetraamide (6) were prepared, and their crystal structures were determined by single-crystal X-ray diffraction method. The steric hindrances posed by tert-butyl groups play an important part in the synthesis and the self-assembly of the two compounds. Compound 6 was synthesized from the corresponding ester, which was obtained by the reaction of acid chloride with ammonia. In the crystal structure, compound 4 presents a highly symmetric molecular structure, while for compound 6, because of absence of tert-butyl groups, it presents a more flexible molecular structure.     

A generalized funk’s section theorem for measures

If L is a star body in R~n whose central(n-i)-slices have the same(n-i)-dimensional measure μ_(n-i)(with appropriate density)as the central(n-i)-slices of an origin-symmetric star body K,then the corresponding n-dimensional measures μ_n of K and L satisfy μ_n(K)≤μ_n(L).This extends a generalized Funk’s section theorem for volumes to that for measures.     

A practical process for the synthesis of translocator protein 18kDa imidazopyridine ligand

In this article, an effective feasible method to synthesize translocator protein 18kDa （TSPO） imidazopyridine ligand 7 is discussed. A new procedure for the synthesis of the key intermediate 17 has been developed in four steps （condensation, diazo reaction, hydrolysis, amidation） from 2-aminopyridine 18. The overall yield was increased from 18% to 31.6%. One of the key steps is using activated copper powder as a catalyst in several cycles. Finally, reduction of 17 with Zn dust completed the synthesis of TSPO imidazopyridine ligand 7 in 86% yield.     

Identification of Markovian open system dynamics for qubit systems

We discuss the problem of identification of the dynamical generators for open two-level quantum systems in a Markovian environment.Based on Bloch sphere representation,the identification problem is converted to the estimation of a 3-dimensional real process matrix A and an inhomogeneous term c.The parameter identifiability and sufficient conditions for completely identification of A and c are obtained.Further discussion shows that the obtained sufficient conditions are not always necessary.The approach can be generalized to finite-level open quantum systems in an arbitary Markovian environment.     

Design, synthesis and nonlinear optical properties of “dendronized hyperbranched polymers”

A new type of dendritic polymer, named dendronized hyperbranched polymer (DHP), was prepared successfully by the macro-monomer approach. Thanks to the perfect 3D isolation effects, DHPG1 exhibited good NLO property with d 33 value of 133 pm/V, higher than its analogues of dendronized polymer and dendrimer, and its stability of NLO effect was also enhanced.     

A new second-order Mehrotra-type predictor-corrector algorithm for SDO

In Zhang's recent works,a second-order Mehrotra-type predictor-corrector algorithm for linear optimization was extended to semidefinite optimization and derived that the algorithm for semidefinite optimization had O(n~(3/2)log(X~0)~T·S~0/ε) iteration complexity based on the NT direction as Newton search direction. In this paper, we extend the second-order Mehrotra-type predictor-corrector algorithm for linear optimization to semidefinite optimization and discuss the polynomial convergence of the algorithm by modifying the corrector direction and new iterates. It is proved that the iteration complexity is reduced to O(n~(3/2)log(X~0)~T·S~0/ε), which coincides with the currently best iteration bound of Mehrotra-type predictor-corrector algorithm for semidefinite optimization.     

Super-Edge-Connectivity of G(k,d,s)(s≥k/2)

A graph G is super-edge-connected,for short super-λ,if every minimum edge-cut consists of edges adjacent to a vertex of minimum degree.Alphabet overlap graph G(k,d,s)is undirected,simple graph with vertex set V={v|v=1()kv…v;vi∈{1,2,…,d},i=1,…,k}.Two vertices u=(u1…uk)and v=(v1…vk)are adjacent if and only if us+i=vi or vs+i=ui(i=1,…,k-s).In particular G(k,d,1)is just an undirected de Bruijn graph.In this paper,we show that the diameter of G(k,d,s)is k s,the girth is 3.Finally,we prove that G(k,d,s)(s≥k/2)is super-λ.     

Influences of the shape of magnetic material on the magnetoelectric properties of the PZT/Metglas composite

In this paper, the influences of the shape of magnetic material on the magnetoelectric(ME) properties of PZT/Metglas magnetoelectric(ME) composites have been investigated. The results indicate that, with the decrease of the waist length(L_w) of the dumbbell-shaped Metglas, the magnetic flux density in the center region and ME coefficients(α_(ME)) of the composites increase, while the optimal bias magnetic field Hdc decreases on the contrary. In an AC magnetic field of 1 kHz, the maximum αME(α_(Max)) of the composite with L_w= 20 mm exhibits 1.3 times larger than that of the one with L_w=50 mm, and the optimal Hdc deceases by 15%. At the resonant frequencies of each composites, α_(Max) is enhanced by 1.3 times as L_w decreases from 50 to 20 mm. The simulation made by Comsol Multiphysics and the theoretical analysis based on an equivalent magnetic circuit confirm the experimental results.     

Generalized Intersection Bodies with Parameter

AIn 2005, the classical intersection bodies and L_p intersection bodies were extended. Afterwards, the concept of general L_p intersection bodies and the generalized intersection bodies was introduced. In this paper, we define the generalized bodies with parameter. Besides, we establish the extremal values for volume, Brunn-Minkowski type inequality for radial combination and L_p harmonic Blaschke combination of this notion.     

Thermodynamic functions and growth constants of web-like ZnO nanostructures

Web-like ZnO nanostructures have been successfully synthesized using the potassium nitrate route at various temperatures to simplify conventional preparation methods. The structures and morphologies of the as-prepared products were characterized by X-ray powder diffraction (XRD) and field-emission scanning electron microscopy (FE-SEM). The results showed that the reaction temperature was an important parameter, and that there was a feedback effect between nano-structure and growth parameters, combined with in situ micro-calorimetry, the reaction rate constants of the three systems were found to have been: 2.43×10-6, 2.70×10-8 and 3.12×10-7s-1 respectively. Furthermore, based on the relationship governing the potential differences between nanoand bulk ZnO, thermodynamic functions of nano-ZnO such as standard molar entropy (Sm,ZnO(nano)), standard molar Gibbs free energy of formation (△rGm,ZnO(nano)), and standard molar enthalpy of formation (△rHm,ZnO(nano)) have been calculated by the electrochemical method.