The preparation of nano sized La 2O 3 powder by mechanochemical reaction of lanthanum carbonate with sodium hydroxide and subsequent heat treatment was studied using X ray diffraction, differential thermal and ther...The preparation of nano sized La 2O 3 powder by mechanochemical reaction of lanthanum carbonate with sodium hydroxide and subsequent heat treatment was studied using X ray diffraction, differential thermal and thermo gravimetric analysis and transmission electron microscopy. It was found that the mechanochemical reaction process can be divided into two steps: the first step is the multi phases mechanochemical reaction of lanthanum carbonate with NaOH to form amorphous lanthanum basic carbonate and lanthanum hydroxide, and the second step is the crystallization of basic lanthanum carbonate with the formula of La 2(OH) 2(CO 3) 2·H 2O under a quasi hydrothermal synthesis condition caused by the mechanical ball milling. The synthesized La 2O 3 powder appears clearly separated spherical like monodisperse nano size particles in which particle size ranges from 30 to 50 nm.展开更多
The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: ...The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: C20H36N10Ni, monoclinic, space group P21/c, a = 9.632(2), b = 11.833(2), c = 10.613(2) ? b = 93.46(3), V = 1207.4(4) ?, Mr = 475.30, Z = 2, Dc = 1.307 g/cm3, F(000) = 508, m(MoKa) = 0.831 mm-1, R = 0.0446 and wR = 0.1274 for 2423 observed reflections with I > 2s(I). The center nickel ion is coordinated by six nitrogen atoms, four from the macrocyclic ligand teta and the other two from two dicyanamides. The dicyanamide is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.展开更多
The complex of [As2VIV8VV2O26]8H2O 1 has been hydrothermally synthesized and characterized by IR, elemental analysis, EPR, TGA and single crystal X-ray diffraction analysis. The structure features of 1 are described.
A new copper(Ⅱ) complex [Cu(PDA)(H 2O) 2] was synthesized and its structure was determined. Cu(Ⅱ) is five coordinated in a tetragonal pyramid geometry. The two coordinating water molecules are different and t...A new copper(Ⅱ) complex [Cu(PDA)(H 2O) 2] was synthesized and its structure was determined. Cu(Ⅱ) is five coordinated in a tetragonal pyramid geometry. The two coordinating water molecules are different and the two Cu-O bond lengths differ by nearly 0.02 nm. The whole crystal is linked to form a three dimensional network by means of hydrogen bonds. The X band ESR spectrum shows three different g tensors with a well resolved hyperfine structure in the g z signal, giving the ESR parameters g x=2 05, g y =2 065 and g z =2 29. The covalency of the coordinate bonds and the deviation from tetragonal pyramid geometry for the complex are discussed based on the ESR spectra.展开更多
A new imidazolium compound, C15H17N4ClO4, was prepared from a flexible bidentate ligand of 1,3-di(imidazol-1-ylmethyl)-5-methylbenzene, and characterized by X-ray analysis. It is of orthorhombic, space group Pnma with...A new imidazolium compound, C15H17N4ClO4, was prepared from a flexible bidentate ligand of 1,3-di(imidazol-1-ylmethyl)-5-methylbenzene, and characterized by X-ray analysis. It is of orthorhombic, space group Pnma with a = 8.182(2), b = 12.874(3), c = 15.611(4) ? V = 1644.4(7) 3, Dc = 1.425 g/cm3, Z = 4, Mr = 352.78, m(MoKa) = 0.944 mm-1, F(000) = 736, S = 1.036, the final R = 0.0521 and wR = 0.1187 for 1128 observed reflections (I > 2s(I)). An infinite one-dimensional zigzag chain is formed by NH…N hydrogen bonding interactions between the imidazolium salt cations.展开更多
Compound [V_ 16 O_ 38 (Cl)][Cu(enMe)_2]_ 3.5 ·2H_2O(1) has been hydrothermally synthesized and characterized by means of single-crystal X-ray diffraction,elemental analysis,IR,EPR and TGA analysis. The X-ray c...Compound [V_ 16 O_ 38 (Cl)][Cu(enMe)_2]_ 3.5 ·2H_2O(1) has been hydrothermally synthesized and characterized by means of single-crystal X-ray diffraction,elemental analysis,IR,EPR and TGA analysis. The X-ray crystallography shows that compound 1 contains a new {V_ 16 O_ 38 } cluster shell,which is connected by [Cu(enMe)_2] 2+ coordination fragments into a 3-D framework. The compound crystallized in a monoclinic system with space group P2(1)/n,M =2235.82,a =1.26076(3) nm,b =2.55802(6) nm,c =2.14742(4) nm,β =90.7380(10)°, V =6.9250(3) nm 3,Z =4,F (000)=4418,D _c=2.145 g·cm -3 , μ =3.227 mm -1 ,( Δ/σ )=0.000,S =1.066.展开更多
A novel compound [H_2Mo_ 5.5V_ 10.5O_ 40(PO_4)][Cu(en)_2]_4·7H_2O(1) was synthesized from V_2O_5, MoO_3, CuCl_2·2H_2O, en, H_3PO4 and H_2O in an aqueous solution via the hydrothermal method and characteri...A novel compound [H_2Mo_ 5.5V_ 10.5O_ 40(PO_4)][Cu(en)_2]_4·7H_2O(1) was synthesized from V_2O_5, MoO_3, CuCl_2·2H_2O, en, H_3PO4 and H_2O in an aqueous solution via the hydrothermal method and characterized by means of single-crystal X-ray diffraction, elemental analyses, IR, EPR spectra and thermal analyses. C_ 16H_ 80Cu_4Mo_ 5.5N_ 16O_ 51PV_ 10.5 crystallized in a triclinic system, the space group is P1 with M=2660.63, a= 1.283590(10) nm, b=1.289910(10) nm, c=1.387870(10) nm, V=1.80942(2) nm 3, Z=2, D_x=4.883 g/cm 3, F(000)=2599, μ=6.956 mm -1, (Δ/σ)=0.000, S=1.089. The crystal structure was solved by the direct methods with the final R=0.0752 and wR=0.1988 for 6311 observed reflections with I≥2σ(I). The X-ray crystallography reveals that compound 1 is a novel two-dimensional framework material constructed from the mixed Mo/V polyoxometalate and coordination groups.展开更多
Dimeric complex 〔Cu(SbPh 3) 2I〕 2 has been synthesized by a solid state reaction at a low heating temperature and its crystal structure has been analyzed by X ray crystallography. The crystal is monoclinic, space gr...Dimeric complex 〔Cu(SbPh 3) 2I〕 2 has been synthesized by a solid state reaction at a low heating temperature and its crystal structure has been analyzed by X ray crystallography. The crystal is monoclinic, space group P2 1/a (#14), a = 20 436(5), b=14.125(3), c=24.683(3) , β=110.67(1)°, Z=4, V =6666(2) 3; C 72 H 60 Sb 4I 2Cu 2, M r = 1792, D c = 1.787 g·cm -3 , μ (Mo Kα ) = 31.88 cm -1 , F(000)=3440, R= 0.038 and R w= 0.043 for 5632 observed reflections ( I≥3.0σ(I) ) and 361 refined parameters. The result reveals the copper and the bridging iodide atoms form an approximately planar rhomboid array. Effects of the bulkiness of the ligands upon the structures of the analogous complexes are discussed.\;展开更多
A stable Pd(II) compound Pd(AETYF)Cl2CH2Cl2 (AETYF = 4?5?diaza-9? (4,5-bis(ethylthio)-1,3-dithiole-2-ylidene)-fluorene) has been synthesized and its crystal structure was determined by X-ray crystallography. The cryst...A stable Pd(II) compound Pd(AETYF)Cl2CH2Cl2 (AETYF = 4?5?diaza-9? (4,5-bis(ethylthio)-1,3-dithiole-2-ylidene)-fluorene) has been synthesized and its crystal structure was determined by X-ray crystallography. The crystal is of monoclinic, space group P21/c with a = 15.249(6), b = 8.619(3), c = 19.078(7) ? b = 106.932(8), C19H18Cl4N2PdS4, Mr = 650.79, V = 2398.6(16) 3, Z = 4, Dc = 1.802 g/cm3, F(000) = 1296, m = 1.579 mm-1, Npar = 268, the final R = 0.0538 and wR = 0.1282 for 5068 observed reflections with I > 2s(I). The crystal structure determi- nation shows that the atoms of the molecule, except two ethyl-groups, are conjugated in a quasi- plane and these molecules are further stacked or contacted via plane to plane or edge to edge p-p interactions, forming parallel molecular chains along the b axis.展开更多
Two new s-triazine derivatives, which belong to linear dipolar type and triangle octupolar type respectively, have been synthesized. The structure of the dipolar compound has been determined by X-ray diffraction. The ...Two new s-triazine derivatives, which belong to linear dipolar type and triangle octupolar type respectively, have been synthesized. The structure of the dipolar compound has been determined by X-ray diffraction. The two-photon absorption cross-section σ, and the two-photon excited fluorescence (TPEF) intensities are increased significantly from dipolar compound to octupolar compound.展开更多
The title compound [Zn(Him2Py)(N3)2]2 (Zn2C26H38N18O2, Mr = 765.48) has been prepared and structurally characterized by X-ray diffraction methods. It crystallizes in monoclinic, space group P21/n with a = 10.989(3), b...The title compound [Zn(Him2Py)(N3)2]2 (Zn2C26H38N18O2, Mr = 765.48) has been prepared and structurally characterized by X-ray diffraction methods. It crystallizes in monoclinic, space group P21/n with a = 10.989(3), b = 11.519(3), c = 13.812(4) ? b = 101.700(5), V = 1711.9(9) ?, Z = 2, Dc = 1.485 g/cm3, m(MoKa) = 1.456 mm～1, F(000) = 792, the final R = 0.0401 and wR = 0.0861 for 2054 observed reflections with I>2s(I). The imino nitroxide 2-(3- methyl-2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl (im2Py) was reduced to obtain 2-(3-methyl -2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-ydroxy (Him2Py) coordinating to the zinc (II) ion, around which the coordination geometry is a square-based pyramid with a terminal nitrogen atom located at the apical position. The four basal sites are occupied by two m1,1 nitrogen atoms from two different bridging azide ions and two nitrogen atoms from Him2Py. The units of [Zn(Him2Py)(N3)2]2 were connected as two dimension planes by intermolecular hydrogen bonds.展开更多
Copper oxalate nanorods were successfully prepared by means of a simple one-step solid-state reaction method with the assistance of a suitable surfactant, polyethylene glycol 400. The product with uniform rod-like mor...Copper oxalate nanorods were successfully prepared by means of a simple one-step solid-state reaction method with the assistance of a suitable surfactant, polyethylene glycol 400. The product with uniform rod-like morphology was characterized by XRD, TEM and SEM. The formational mechanism of the rod-like structure was also preliminary discussed.展开更多
The pair correlation energy of bonding electrons is used and analyzed in the cal- culation of CH and CY (Y = F, O, N) bonding electron pairs in CH3X (X = F, OH, NH2) isoelec- tronic systems based on intra- and interpa...The pair correlation energy of bonding electrons is used and analyzed in the cal- culation of CH and CY (Y = F, O, N) bonding electron pairs in CH3X (X = F, OH, NH2) isoelec- tronic systems based on intra- and interpair correlation energy results at both MP2-OPT2/6- 311++G(d) and MP2-OPT2/cc-pVtz levels with MELD program. Comparison of two set results shows that cc-pVtz and 6-311++G(d) give more correlation energy of valence electrons and innermost core electron pairs, respectively in these systems, resulting that the total correlation energy with cc-pVtz basis of each system is larger than that with 6-311++G(d). Investigations of pair correlation energy show that with the decrease of electronegativity of X atom and the increase of H atoms in these CH3X (X = F, OH, NH2) systems, the pair correlation energy of 1sC2 of the C atoms is transferable, and the correlation energy of CH bonding electron pair with little changes is of approximate transferability, while those of CY (CF, CO, CN) bonding electron pair decrease in a large extent from CH3F through CH3OH to CH3NH2 molecules. It is suggested that the study of pair correlation energy of bonding electrons will further deepen the understanding of electron corre- lation effect from traditional chemical bonding concept.展开更多
A novel complex [Ag(NIT3Py)3]?(ClO4)(H2O) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the rhombohedral system, space group R 3 with a = 15.8227(17), b = 15.8227(...A novel complex [Ag(NIT3Py)3]?(ClO4)(H2O) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the rhombohedral system, space group R 3 with a = 15.8227(17), b = 15.8227(17), c = 31.445(3) ?, γ = 120°, V = 6817.8(12) ?3, Dc = 1.370 g/cm3, Z = 6, μ = 0.566 mm-1, Mr = 937.18, F(000) = 2916, R = 0.0715, wR = 0.2115 and GOF = 1.086. The structure consists of Ag(NIT3Py)3+ cation moiety, one water molecule and one perchloric ion. The Ag(I) ion is in a trigonal planar coordination environment formed by three nitrogen atoms from three NIT3Py ligand molecules.展开更多
The title compound [Cu(Phen)3](ClO4)2(btio)(H2O), where btio = 2-(4- benzoyloxyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, has been prepared and structurally characterized by X-ray diffraction. It crystallizes i...The title compound [Cu(Phen)3](ClO4)2(btio)(H2O), where btio = 2-(4- benzoyloxyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P?with a = 13.049(4), b = 13.827(5), c = 14.860(5) , a = 71.736(6), b = 77.076(6), g = 87.054(6)? C50H43Cl2CuN8O13, Mr = 1098.36, V = 2481(1) 3, Z = 2, Dc = 1.470 g/cm3, m(MoKa) = 0.622 mm-1, F(000) = 1132, the final R = 0.0639 and wR = 0.1473 for 8705 independent reflections with Rint =0.0285. The title compound is composed of [Cu(Phen)3]2+ moiety , one btio, two perchlorate ions and one water molecule. The copper(II) ion is octahedrally coordinated by three 1,10-phenanthroline ligands. The outer sphere consisting of one btio, two perchlorate ions and one water molecule is combined with the inner by hydrogen bonds and electrostatic interactions.展开更多
Based on the quantum chemical study of the silylidyne insertion reaction with NH3 or PH3, the general statistical thermodynamics and Eyring transition state theory with Wigner correction are used to compute the change...Based on the quantum chemical study of the silylidyne insertion reaction with NH3 or PH3, the general statistical thermodynamics and Eyring transition state theory with Wigner correction are used to compute the changes of thermodynamic functions, equilibrium constants, A factors and rate constants of the two reactions in the temperature range 200-2000K. The results show that both of these reactions are thermodynamically dominant at low temperatures and kinetically favored at higher temperatures. The comparison between these two reactions shows that the SiH reaction with NH3 is more exothermic than SiH with PH3, while the rate constant of SiH reaction with NH3 is lower than that of SiH with PH3 at the same temperature.展开更多
A new compound 1,1?-bis(3-pyridyl)-propylene(3,7-diformyl-N-ethylpheno- thiazinyl)ketone (C30H23N3O2S, Mr = 489.4) has been synthesized, and its crystal structure was determined by single-crystal X-ray diffraction met...A new compound 1,1?-bis(3-pyridyl)-propylene(3,7-diformyl-N-ethylpheno- thiazinyl)ketone (C30H23N3O2S, Mr = 489.4) has been synthesized, and its crystal structure was determined by single-crystal X-ray diffraction method. The crystal is of orthorhombic, space group Ima2 with a = 27.491(5), b = 11.942(2), c = 7.389(2) ?, V = 2425.8(7) ?3, Z = 8, Dc = 1.340 g/cm3, μ = 0.167 mm-1, F(000) = 1024, the final R = 0.0363 and wR = 0.0869 for 2054 unique reflections with Rint = 0.0254. The structural determination shows that the molecule assumes a butterfly configuration with nearly planar wings. In addition, the electrochemical study indicates that there is a high electronic delocalization in the molecule.展开更多
A novel complex [Cd2(phen)4(fca)2](ClO4)2(H2O)2 (fca = dianion of 3-ferrocenyl- 2-crotonic acid, phen = 1,10-phenanthroline) has been synthesized and characterized by X-ray single-crystal structure analysis. It crysta...A novel complex [Cd2(phen)4(fca)2](ClO4)2(H2O)2 (fca = dianion of 3-ferrocenyl- 2-crotonic acid, phen = 1,10-phenanthroline) has been synthesized and characterized by X-ray single-crystal structure analysis. It crystallizes in triclinic system, space group P?with a = 11.6297(5), b = 12.5165(5), c = 13.8986(6) ? a = 63.345(1), b = 87.747(1), g = 71.862(1), V = 1706.20(1) ?, Z = 1, Dc = 1.673 g/cm3, F(000) = 868 and m(MoKa) = 1.185 mm-1 (l = 0.71073 ). R = 0.0800 and wR = 0.1793 for 7653 observed reflections (I > 2s(I)). The structure consists of a dinuclear cation [Cd2(phen)4(fca)2]2+, two discrete perchlorate anions and two water molecules. The cationic part of the complex shows a tetrametallic core in which two fca groups act as the (O, O) bridging ligands between two cadmium(Ⅱ) ions with a distorted octahedral environment. The Cd…Cd intradimer distance is 4.128 ?展开更多
文摘The preparation of nano sized La 2O 3 powder by mechanochemical reaction of lanthanum carbonate with sodium hydroxide and subsequent heat treatment was studied using X ray diffraction, differential thermal and thermo gravimetric analysis and transmission electron microscopy. It was found that the mechanochemical reaction process can be divided into two steps: the first step is the multi phases mechanochemical reaction of lanthanum carbonate with NaOH to form amorphous lanthanum basic carbonate and lanthanum hydroxide, and the second step is the crystallization of basic lanthanum carbonate with the formula of La 2(OH) 2(CO 3) 2·H 2O under a quasi hydrothermal synthesis condition caused by the mechanical ball milling. The synthesized La 2O 3 powder appears clearly separated spherical like monodisperse nano size particles in which particle size ranges from 30 to 50 nm.
基金The project was supported by the funds of the Key Laboratory of Organic Syntheses of Jiangsu province(KJS01018) and Funds of Young Teacher of Suzhou University
文摘The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: C20H36N10Ni, monoclinic, space group P21/c, a = 9.632(2), b = 11.833(2), c = 10.613(2) ? b = 93.46(3), V = 1207.4(4) ?, Mr = 475.30, Z = 2, Dc = 1.307 g/cm3, F(000) = 508, m(MoKa) = 0.831 mm-1, R = 0.0446 and wR = 0.1274 for 2423 observed reflections with I > 2s(I). The center nickel ion is coordinated by six nitrogen atoms, four from the macrocyclic ligand teta and the other two from two dicyanamides. The dicyanamide is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.
文摘The complex of [As2VIV8VV2O26]8H2O 1 has been hydrothermally synthesized and characterized by IR, elemental analysis, EPR, TGA and single crystal X-ray diffraction analysis. The structure features of 1 are described.
基金Supported by the National Natural Science Foundation of China(No.2 0 0 710 192 0 0 710 2 0 and5 0 172 0 2 ) and the Re-search Fund for Doctoral Program of Higher Education.
文摘A new copper(Ⅱ) complex [Cu(PDA)(H 2O) 2] was synthesized and its structure was determined. Cu(Ⅱ) is five coordinated in a tetragonal pyramid geometry. The two coordinating water molecules are different and the two Cu-O bond lengths differ by nearly 0.02 nm. The whole crystal is linked to form a three dimensional network by means of hydrogen bonds. The X band ESR spectrum shows three different g tensors with a well resolved hyperfine structure in the g z signal, giving the ESR parameters g x=2 05, g y =2 065 and g z =2 29. The covalency of the coordinate bonds and the deviation from tetragonal pyramid geometry for the complex are discussed based on the ESR spectra.
基金the Natural Science Foundation of Jiangsu province (Grant No Bk2001031)
文摘A new imidazolium compound, C15H17N4ClO4, was prepared from a flexible bidentate ligand of 1,3-di(imidazol-1-ylmethyl)-5-methylbenzene, and characterized by X-ray analysis. It is of orthorhombic, space group Pnma with a = 8.182(2), b = 12.874(3), c = 15.611(4) ? V = 1644.4(7) 3, Dc = 1.425 g/cm3, Z = 4, Mr = 352.78, m(MoKa) = 0.944 mm-1, F(000) = 736, S = 1.036, the final R = 0.0521 and wR = 0.1187 for 1128 observed reflections (I > 2s(I)). An infinite one-dimensional zigzag chain is formed by NH…N hydrogen bonding interactions between the imidazolium salt cations.
文摘Compound [V_ 16 O_ 38 (Cl)][Cu(enMe)_2]_ 3.5 ·2H_2O(1) has been hydrothermally synthesized and characterized by means of single-crystal X-ray diffraction,elemental analysis,IR,EPR and TGA analysis. The X-ray crystallography shows that compound 1 contains a new {V_ 16 O_ 38 } cluster shell,which is connected by [Cu(enMe)_2] 2+ coordination fragments into a 3-D framework. The compound crystallized in a monoclinic system with space group P2(1)/n,M =2235.82,a =1.26076(3) nm,b =2.55802(6) nm,c =2.14742(4) nm,β =90.7380(10)°, V =6.9250(3) nm 3,Z =4,F (000)=4418,D _c=2.145 g·cm -3 , μ =3.227 mm -1 ,( Δ/σ )=0.000,S =1.066.
文摘A novel compound [H_2Mo_ 5.5V_ 10.5O_ 40(PO_4)][Cu(en)_2]_4·7H_2O(1) was synthesized from V_2O_5, MoO_3, CuCl_2·2H_2O, en, H_3PO4 and H_2O in an aqueous solution via the hydrothermal method and characterized by means of single-crystal X-ray diffraction, elemental analyses, IR, EPR spectra and thermal analyses. C_ 16H_ 80Cu_4Mo_ 5.5N_ 16O_ 51PV_ 10.5 crystallized in a triclinic system, the space group is P1 with M=2660.63, a= 1.283590(10) nm, b=1.289910(10) nm, c=1.387870(10) nm, V=1.80942(2) nm 3, Z=2, D_x=4.883 g/cm 3, F(000)=2599, μ=6.956 mm -1, (Δ/σ)=0.000, S=1.089. The crystal structure was solved by the direct methods with the final R=0.0752 and wR=0.1988 for 6311 observed reflections with I≥2σ(I). The X-ray crystallography reveals that compound 1 is a novel two-dimensional framework material constructed from the mixed Mo/V polyoxometalate and coordination groups.
文摘Dimeric complex 〔Cu(SbPh 3) 2I〕 2 has been synthesized by a solid state reaction at a low heating temperature and its crystal structure has been analyzed by X ray crystallography. The crystal is monoclinic, space group P2 1/a (#14), a = 20 436(5), b=14.125(3), c=24.683(3) , β=110.67(1)°, Z=4, V =6666(2) 3; C 72 H 60 Sb 4I 2Cu 2, M r = 1792, D c = 1.787 g·cm -3 , μ (Mo Kα ) = 31.88 cm -1 , F(000)=3440, R= 0.038 and R w= 0.043 for 5632 observed reflections ( I≥3.0σ(I) ) and 361 refined parameters. The result reveals the copper and the bridging iodide atoms form an approximately planar rhomboid array. Effects of the bulkiness of the ligands upon the structures of the analogous complexes are discussed.\;
基金the National Natural Science Foundation of China (20071024 20371033) and Suzhou University
文摘A stable Pd(II) compound Pd(AETYF)Cl2CH2Cl2 (AETYF = 4?5?diaza-9? (4,5-bis(ethylthio)-1,3-dithiole-2-ylidene)-fluorene) has been synthesized and its crystal structure was determined by X-ray crystallography. The crystal is of monoclinic, space group P21/c with a = 15.249(6), b = 8.619(3), c = 19.078(7) ? b = 106.932(8), C19H18Cl4N2PdS4, Mr = 650.79, V = 2398.6(16) 3, Z = 4, Dc = 1.802 g/cm3, F(000) = 1296, m = 1.579 mm-1, Npar = 268, the final R = 0.0538 and wR = 0.1282 for 5068 observed reflections with I > 2s(I). The crystal structure determi- nation shows that the atoms of the molecule, except two ethyl-groups, are conjugated in a quasi- plane and these molecules are further stacked or contacted via plane to plane or edge to edge p-p interactions, forming parallel molecular chains along the b axis.
基金supported by the National Natural Science Foundation of China(No.20172034,20472044)the Ph.D.Programs Foundation of Ministry of Education of China
文摘Two new s-triazine derivatives, which belong to linear dipolar type and triangle octupolar type respectively, have been synthesized. The structure of the dipolar compound has been determined by X-ray diffraction. The two-photon absorption cross-section σ, and the two-photon excited fluorescence (TPEF) intensities are increased significantly from dipolar compound to octupolar compound.
基金This work was supported by the National Natural Science Foundation of China (No. 20171025 and No. 90101028)
文摘The title compound [Zn(Him2Py)(N3)2]2 (Zn2C26H38N18O2, Mr = 765.48) has been prepared and structurally characterized by X-ray diffraction methods. It crystallizes in monoclinic, space group P21/n with a = 10.989(3), b = 11.519(3), c = 13.812(4) ? b = 101.700(5), V = 1711.9(9) ?, Z = 2, Dc = 1.485 g/cm3, m(MoKa) = 1.456 mm～1, F(000) = 792, the final R = 0.0401 and wR = 0.0861 for 2054 observed reflections with I>2s(I). The imino nitroxide 2-(3- methyl-2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl (im2Py) was reduced to obtain 2-(3-methyl -2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-ydroxy (Him2Py) coordinating to the zinc (II) ion, around which the coordination geometry is a square-based pyramid with a terminal nitrogen atom located at the apical position. The four basal sites are occupied by two m1,1 nitrogen atoms from two different bridging azide ions and two nitrogen atoms from Him2Py. The units of [Zn(Him2Py)(N3)2]2 were connected as two dimension planes by intermolecular hydrogen bonds.
文摘Copper oxalate nanorods were successfully prepared by means of a simple one-step solid-state reaction method with the assistance of a suitable surfactant, polyethylene glycol 400. The product with uniform rod-like morphology was characterized by XRD, TEM and SEM. The formational mechanism of the rod-like structure was also preliminary discussed.
基金Supported by the National Natural Science Foundation of China (No. 20173027 and No. 29873023)
文摘The pair correlation energy of bonding electrons is used and analyzed in the cal- culation of CH and CY (Y = F, O, N) bonding electron pairs in CH3X (X = F, OH, NH2) isoelec- tronic systems based on intra- and interpair correlation energy results at both MP2-OPT2/6- 311++G(d) and MP2-OPT2/cc-pVtz levels with MELD program. Comparison of two set results shows that cc-pVtz and 6-311++G(d) give more correlation energy of valence electrons and innermost core electron pairs, respectively in these systems, resulting that the total correlation energy with cc-pVtz basis of each system is larger than that with 6-311++G(d). Investigations of pair correlation energy show that with the decrease of electronegativity of X atom and the increase of H atoms in these CH3X (X = F, OH, NH2) systems, the pair correlation energy of 1sC2 of the C atoms is transferable, and the correlation energy of CH bonding electron pair with little changes is of approximate transferability, while those of CY (CF, CO, CN) bonding electron pair decrease in a large extent from CH3F through CH3OH to CH3NH2 molecules. It is suggested that the study of pair correlation energy of bonding electrons will further deepen the understanding of electron corre- lation effect from traditional chemical bonding concept.
基金This work was supported by the National Natural Science Foundation of China (No. 20331010) and Natural Science Foundation (No.033602011) of Tianjin
文摘A novel complex [Ag(NIT3Py)3]?(ClO4)(H2O) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the rhombohedral system, space group R 3 with a = 15.8227(17), b = 15.8227(17), c = 31.445(3) ?, γ = 120°, V = 6817.8(12) ?3, Dc = 1.370 g/cm3, Z = 6, μ = 0.566 mm-1, Mr = 937.18, F(000) = 2916, R = 0.0715, wR = 0.2115 and GOF = 1.086. The structure consists of Ag(NIT3Py)3+ cation moiety, one water molecule and one perchloric ion. The Ag(I) ion is in a trigonal planar coordination environment formed by three nitrogen atoms from three NIT3Py ligand molecules.
基金This work was supported by the National Natural Science Foundation of China (No. 20171025 and No. 20331010)
文摘The title compound [Cu(Phen)3](ClO4)2(btio)(H2O), where btio = 2-(4- benzoyloxyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P?with a = 13.049(4), b = 13.827(5), c = 14.860(5) , a = 71.736(6), b = 77.076(6), g = 87.054(6)? C50H43Cl2CuN8O13, Mr = 1098.36, V = 2481(1) 3, Z = 2, Dc = 1.470 g/cm3, m(MoKa) = 0.622 mm-1, F(000) = 1132, the final R = 0.0639 and wR = 0.1473 for 8705 independent reflections with Rint =0.0285. The title compound is composed of [Cu(Phen)3]2+ moiety , one btio, two perchlorate ions and one water molecule. The copper(II) ion is octahedrally coordinated by three 1,10-phenanthroline ligands. The outer sphere consisting of one btio, two perchlorate ions and one water molecule is combined with the inner by hydrogen bonds and electrostatic interactions.
文摘Based on the quantum chemical study of the silylidyne insertion reaction with NH3 or PH3, the general statistical thermodynamics and Eyring transition state theory with Wigner correction are used to compute the changes of thermodynamic functions, equilibrium constants, A factors and rate constants of the two reactions in the temperature range 200-2000K. The results show that both of these reactions are thermodynamically dominant at low temperatures and kinetically favored at higher temperatures. The comparison between these two reactions shows that the SiH reaction with NH3 is more exothermic than SiH with PH3, while the rate constant of SiH reaction with NH3 is lower than that of SiH with PH3 at the same temperature.
基金This work was supported by the National Natural Science Foundation of China (50272001, 50335050) and the Committee of Education of Anhui Province (2004KJ020, 2003KJ218)
文摘A new compound 1,1?-bis(3-pyridyl)-propylene(3,7-diformyl-N-ethylpheno- thiazinyl)ketone (C30H23N3O2S, Mr = 489.4) has been synthesized, and its crystal structure was determined by single-crystal X-ray diffraction method. The crystal is of orthorhombic, space group Ima2 with a = 27.491(5), b = 11.942(2), c = 7.389(2) ?, V = 2425.8(7) ?3, Z = 8, Dc = 1.340 g/cm3, μ = 0.167 mm-1, F(000) = 1024, the final R = 0.0363 and wR = 0.0869 for 2054 unique reflections with Rint = 0.0254. The structural determination shows that the molecule assumes a butterfly configuration with nearly planar wings. In addition, the electrochemical study indicates that there is a high electronic delocalization in the molecule.
基金the grants from the State Key Program of China the National Natural Science Foundation of China (29871001 20071001) and the Committee of Education of Anhui province
文摘A novel complex [Cd2(phen)4(fca)2](ClO4)2(H2O)2 (fca = dianion of 3-ferrocenyl- 2-crotonic acid, phen = 1,10-phenanthroline) has been synthesized and characterized by X-ray single-crystal structure analysis. It crystallizes in triclinic system, space group P?with a = 11.6297(5), b = 12.5165(5), c = 13.8986(6) ? a = 63.345(1), b = 87.747(1), g = 71.862(1), V = 1706.20(1) ?, Z = 1, Dc = 1.673 g/cm3, F(000) = 868 and m(MoKa) = 1.185 mm-1 (l = 0.71073 ). R = 0.0800 and wR = 0.1793 for 7653 observed reflections (I > 2s(I)). The structure consists of a dinuclear cation [Cd2(phen)4(fca)2]2+, two discrete perchlorate anions and two water molecules. The cationic part of the complex shows a tetrametallic core in which two fca groups act as the (O, O) bridging ligands between two cadmium(Ⅱ) ions with a distorted octahedral environment. The Cd…Cd intradimer distance is 4.128 ?
