Hydrogen-bonded polymer complex films with the thickness ranging from 50 nm to 2400 nm were prepared by layer-by-layer （LbL） assembly of poly（2-ethyl-2-oxazoline） （PEOX） and poly（acrylic acid） （PAA）. The dew...Hydrogen-bonded polymer complex films with the thickness ranging from 50 nm to 2400 nm were prepared by layer-by-layer （LbL） assembly of poly（2-ethyl-2-oxazoline） （PEOX） and poly（acrylic acid） （PAA）. The dewetting behavior of PEOX/PAA films under hydrothermal condition was investigated. It was found that the dewetting occurred at solid-liquid interface, and the typical morphologies such as holes, irregular cellular structure, and droplets were observed. Atomic force microscopy （AFM） revealed the initial rupture of the film. Microscopic Raman and infrared （IR） imaging demonstrated that the PEOX and PAA chains remained association during the dewetting process.展开更多
The novel complex{[Co(bipy)(azpy)_(2)(NCS)_(2)]·H_(2)O}n(where bipy=4,4′bipyridine,azpy=4,4′azobisp yridine)has been synthesized and characterized by elemental analyses,IR,UV,thermal analyses,and variable tempe...The novel complex{[Co(bipy)(azpy)_(2)(NCS)_(2)]·H_(2)O}n(where bipy=4,4′bipyridine,azpy=4,4′azobisp yridine)has been synthesized and characterized by elemental analyses,IR,UV,thermal analyses,and variable temperature magnetic susceptibility.The crystal(C_(32)H_(26)CoN_(12)OS_(2),Mr=717.70)belongs to the orthorhombic,space group Pnna,a=2.21312(16)nm,b=1.40403(10)nm,c=1.14237(8)nm,V=3.5497(4)nm^(3),Z=4,Dc=1.343g·cm^(-3),μ=0.645mm^(-1),F(000)=1476,and final R_(1)=0.0691,wR_(2)=0.1129 for 231 parameters and 1674 observed reflections[I>2.00σ(I)].The Co(Ⅱ)atom is,in a distorted octahedral geometry,coordinated by six nitrogen atoms from two bridging bipy,two monodentate azpy,and two thiocyanate groups.The bridging ligand bipy links Co(Ⅱ)atoms to form the infinite“rod"with terminal coordination azpy ligand acting as sidearms.Unprecedented three parallel interpenetrating two dimensional(4,4)networks and novel infinite triple helices are formed via hydrogen bonding interactions.CCDC:155588.展开更多
Crystalline coordination complexes of actinides,especially in atypical oxidation states,are not only fundamentally important for expanding the notably limited knowledge on the bonding nature of actinides but could als...Crystalline coordination complexes of actinides,especially in atypical oxidation states,are not only fundamentally important for expanding the notably limited knowledge on the bonding nature of actinides but could also provide critical information toward the development of nuclear fuel cycle,waste management,and national security.Plutonium(Pu)is the only element in the periodic table that could exist in four oxidation states in aqueous solutions simultaneously.展开更多
A novel complex [Cd2（phen）4（phth）2]·4H2O has been synthesized by the reaction of Hzphth（phthalic acid） and phen（1,10-phenanthroline） with Cd（Ⅱ） in ethanol-water solution. X-ray crystal structure analys...A novel complex [Cd2（phen）4（phth）2]·4H2O has been synthesized by the reaction of Hzphth（phthalic acid） and phen（1,10-phenanthroline） with Cd（Ⅱ） in ethanol-water solution. X-ray crystal structure analysis shows it crystallizes in triclinic, space group PI- with a = 10.619（3）, b = 12.560（4）, c = 12.651（4） A, a = 98.775（5）, β = 109.035（5）,γ = 113-576（5）°, C32H24CdN4O6, Mr= 672.95, V = 1381.7（7）A^3, Rint = 0.0358, Z = 2, Dc= 1.618 g/cm^3,μ = 0.845 mm^-1, -6 ≤h≤13, -15 ≤k ≤13, -15 ≤l≤14, F（000） = 680, S = 1.038, R = 0.0480 and wR = 0.0849 for 3992 observed reflections （1 〉 2σ（Ⅰ））. Phth bridges Cd（Ⅱ） to form a macrocyclic compound, and a 2D supramolecular motif is formed through hydrogen bonds and π-π interaction.展开更多
Previously we successfully prepared poly(vinyldiaminotriazine)(PVDT)-based non-viral vectors which complexed plasmid DNA via hydrogen bonding with adenine-thymine base pairs. In this report, surface charges and comple...Previously we successfully prepared poly(vinyldiaminotriazine)(PVDT)-based non-viral vectors which complexed plasmid DNA via hydrogen bonding with adenine-thymine base pairs. In this report, surface charges and complex sizes of this system were further examined. The results showed that PVDT-based polymer could cover surface charges of DNA resulting in slightly negative or neutral complexes. It was also found that the complex sizes were governed by two events: the aggregation induced by the insta-bility of neutral particles, and more compact complexes produced by PVDT-based polymers. In the study of cellular uptake, chlorpromazine and filipin Ⅲ were used to inhibit clathrin- and caveolae-me- diated endocytosis, respectively. We found that PVDT-based systems were transported into cells via a non-clathrin, non-caveolae mediated endocytosis. This special process was studied by temperature inhibition and kinetics assays. It was revealed that such a pathway was characterized by (i) a more en-ergy dependent process and (ii) a much slow transfection-effective internalization.展开更多
A novel mixed oxamate copper(Ⅱ) complex \[Cu(phen)(om)(H 2O)\]·H 2O has been obtained and its structure was determined. The complex crystallizes in monoclinic, space group P2(1)/n, a= 0.845 3(0) nm, b=0.971 2(1)...A novel mixed oxamate copper(Ⅱ) complex \[Cu(phen)(om)(H 2O)\]·H 2O has been obtained and its structure was determined. The complex crystallizes in monoclinic, space group P2(1)/n, a= 0.845 3(0) nm, b=0.971 2(1) nm, c=1.742(1) nm, β=103.89(3)°, V=1.388(0) nm 3, Z=4, R=0.045 8. The copper atom is five-coordinated with a tetragonal pyramid geometry, the complex molecules are linked to form a one-dimensional network via hydrogen bonding. Its X-band EPR spectrum shows an unsymmetric broad signal with g-tensor value 2.12. The IR, TGA and DTA results are also reported. Thermal degradation of the complex starts at 50 ℃ to loss water.展开更多
The single crystal of bi（8-hydroxyquinoline） bihydrated cobalt （Ⅱ） complex, [ Co（Q）2 （H2O2 ] （Q = 8-hydroxyquinoline ion）, has been synthesized by general method and structurally characterized by single crys...The single crystal of bi（8-hydroxyquinoline） bihydrated cobalt （Ⅱ） complex, [ Co（Q）2 （H2O2 ] （Q = 8-hydroxyquinoline ion）, has been synthesized by general method and structurally characterized by single crystal X-ray diffraction. Crystal data： C18H16CoN2O4, monoclinic, C2/c, α = 1.336 2（4） nm, b = 0.941 2（3） nm, c = 1.354 3（4） nm, β= 109.672（4）°, Z = 4. In the complex, Co（ Ⅱ ） ion is six-coordinated, forming a distorted octahedron. H-bonding and π-π stacking interaction play a significant role to form and stabilize the three-dimensional structure.展开更多
The electronic structures of several dinuclears and trinuclears of molybdenum containing thiolates complexes have been calculated by quantum chemistry SCC-DV-Xa method, and the reactivity of complexes has been analy...The electronic structures of several dinuclears and trinuclears of molybdenum containing thiolates complexes have been calculated by quantum chemistry SCC-DV-Xa method, and the reactivity of complexes has been analyzed in terms of the molecular orbital energy level diagrams, orbital characters and charge populations.展开更多
A new La（Ⅲ） complex, {[La（L）（NO3）（H2O）3]·H2O}n （L = 1,10-phenanthroline- 2,9-dicarboxylate）, has been synthesized and structurally determined by X-ray diffraction analysis. The complex crystallizes in ...A new La（Ⅲ） complex, {[La（L）（NO3）（H2O）3]·H2O}n （L = 1,10-phenanthroline- 2,9-dicarboxylate）, has been synthesized and structurally determined by X-ray diffraction analysis. The complex crystallizes in the monoclinic system, space group P21/c with a = 7.7358（17）, b = 8.1664（18）, c = 28.271（6） A, β= 95.184（4）°, V= 1778.6（7） A3, Z = 4, C14H14LaN3O11, Mr = 539.19, Dc = 2.014 g/cm^3, μ= 2.471 mm^-1, F（000） = 1056, the final R = 0.0350 and wR = 0.0659. In this complex, each metal center adopts a ten-coordination geometry formed by two N atoms from a ligand L and eight O atoms from three H2O molecules, a nitrate ion and carboxylates of two ligands. Each ligand adopts a N2,O3-pentdentate coordination mode using two N and two O atoms chelating a La（Ⅲ）, and using another O atom of carboxylate to bridge another La（Ⅲ） center resulting in a 1D helical chain molecule. Intermolecular strong O-H…O and weak C-H…O hydrogen bonds extend the 1D chain structure into a 3D supramolecular architecture.展开更多
The reactions of imidazoquinoxaline and 1,3,5-H3 btc acid under different condition have been investigated. The different degree of hydrolysis reaction leads to two different adducts being produced, namely, [（Hdiam Q...The reactions of imidazoquinoxaline and 1,3,5-H3 btc acid under different condition have been investigated. The different degree of hydrolysis reaction leads to two different adducts being produced, namely, [（Hdiam Quin）＋（H2btc）-]（1）, and [（diam Quin）4（Imi Quin）·4H2O]（2）. Both compounds were characterized by X-ray crystallography. Crystal data for 1： monoclinic, space group Pn with a = 9.868（2）, b = 5.3172（11）, c = 15.387（3）A, β = 91.10（3）°, C17H14N4O6, Mr = 370.32, V = 807.2（3）A3, Z = 2, Dc = 1.524 g/cm3, μ（Mo Kα） = 0.118 mm-1, F（000） = 384, the final R = 0.0385 and w R = 0.0869 for 2294 observed reflections（I 〉 2σ（I））. Crystal data for 2： triclinic, space group P1 with a = 9.825（2）, b = 14.144（3）, c = 16.054（3） A, α = 101.06（3）, β = 102.55（3）, γ = 92.46（3）°, C（44）H40N（20）O4, Mr = 912.96, V = 2128.8（7） A3, Z = 2, Dc = 1.424 g/cm3, μ（Mo Kα） = 0.099 mm-1, F（000） = 952, the final R = 0.0554 and w R = 0.1662 for 6563 observed reflections（I 〉 2σ（I））. X-ray diffraction analysis reveals that compound 1 is a salt. Imidazoquinoxaline was wholly hydrolyzed into 2,3-diaminoquinoxaline and protonated as a cation with H2btc-acting as an anion. However, in compound 2, the imidazoquinoxaline is only partly hydrolyzed, and the resulting 2,3-diaminoquinoxaline forms adduct with the intacted imidazoquinoxaline. Both are further aggregated into 3D frameworks by strong hydrogen bonding even π-π interactions.展开更多
The metal alkoxides are very important in the following two respects: (ⅰ) In contrary with the ordinary pi-acceptor ligands which can stabilize metal ions in low oxidation states, the alkoxide ligands can stabilize d...The metal alkoxides are very important in the following two respects: (ⅰ) In contrary with the ordinary pi-acceptor ligands which can stabilize metal ions in low oxidation states, the alkoxide ligands can stabilize d-electron poor metals in high oxidation state. Steric control of coordination number of the central metal ion and the binding sites with展开更多
The complex [Tm（TBTA）1.5（bipy）（H2O）2]n （H2TBTA = 2,3,5,6-tetrabromoterephthalic acid, bipy = 2,2-bipyridyl） has been synthesized in water-methanol solution at ambient temperature and characterized by single-cr...The complex [Tm（TBTA）1.5（bipy）（H2O）2]n （H2TBTA = 2,3,5,6-tetrabromoterephthalic acid, bipy = 2,2-bipyridyl） has been synthesized in water-methanol solution at ambient temperature and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum and thermogravimetric analysis. The crystal belongs to triclinic, space group P1 with a = 11.1429（2）, b = 11.485（2）, c = 12.872（2）, V = 1498.1（5）3 , Z = 2, C22H14Br6N2O9Tm, Mr = 1098.74, Dc = 2.436 g/cm3 , μ（MoKα） = 11.013 mm-1 , F（000） = 1022, T = 296.15 K, the final R （I 〉2σ（I）） = 0.0494 and wR （all data） = 0.1246. The asymmetric unit of the complex is composed of one Tm ion, one and a half of coordinated TBTA 2-anions, one bipy, two coordinated and one lattice water molecules. The adjacent metal ions are bridged by TBTA 2- anions to form a 2D wave-like layer.展开更多
A coordination polymer of [Zn(BBP)(p-CPOA)]n (where BBP is 2,6-bis(benzimidazolyl)pyridine and p-CPOA is p-carboxylato-phenoxyacetate dianion) has been synthesized and characterized by elemental analysis,IR,TG,and the...A coordination polymer of [Zn(BBP)(p-CPOA)]n (where BBP is 2,6-bis(benzimidazolyl)pyridine and p-CPOA is p-carboxylato-phenoxyacetate dianion) has been synthesized and characterized by elemental analysis,IR,TG,and the single crystal structure was determined by X-ray diffraction. The crystal crystallizes in the monoclinic system,space group of P21/n with a=1.397 3(4) nm,b=1.138 4(3) nm,c=1.575 9(5) nm,β=91.805(1)°,V=2.505 4(13) nm3,Z=4,Dc=1.513 g·cm-3,μ=1.030 mm-1 and F(000)=1 168. Zn(Ⅱ) ion is penta-coordinated and surrounded by two carboxylate O atoms from two different p-CPOA groups in a bis-monodentate mode,three N atoms from the 2,6-bis(benzimidazolyl)pyridine ligand,completing a distorted trigonal bipyramidal coordination configuration. The structure is a helix with a long pitch of 1.138 4 nm. Under direction of supramolecular recognition and attraction,the adjacent chains are formed the double-stranded chain through π-π stacking between the 2,6-bis(benzimidazolyl)pyridine ligands and hydrogen-bonding interactions. A three-dimensional supramolecular network is further constructed through these interactions between the helices. The TG shows that its chain skeleton is thermally stable up to 382 ℃.展开更多
Binuclear transition metal carbonyl clusters serve as the simplest models in understand- ing metal-metal and ligand bonding that are important organometallic chemistry catalysis. Binuclear first row transition metal c...Binuclear transition metal carbonyl clusters serve as the simplest models in understand- ing metal-metal and ligand bonding that are important organometallic chemistry catalysis. Binuclear first row transition metal carbonyl ions are produced via a pulsed laser vaporiza- tion/supersonic expansion cluster ion source in the gas phase. These ions are studied by mass-selected infrared photodissociation spectroscopy in the carbonyl stretching frequency region. Density functional theory calculations have been performed on the geometric struc- tures and vibrational spectra of the carbonyl ions. Their geometric and electronic structures are determined by comparison of the experimental IR spectra with the simulated spectra. The structure and the metM-metal and metal-CO bonding of both saturated and unsaturated homonuclear as well as heteronuclear carbonyl cluster cations and anions are discussed.展开更多
The hydrothermal reaction of isonicotinic acid (4-C5H4N-COOH), Cu(ClO4)(2). 6H(2)O and water at 170 degreesC gave the title compound, [Cu(OH)(2)(H2O)(2)(4-C5H4N-COOH)(2)] (1), which was analyzed by single-crystal X-ra...The hydrothermal reaction of isonicotinic acid (4-C5H4N-COOH), Cu(ClO4)(2). 6H(2)O and water at 170 degreesC gave the title compound, [Cu(OH)(2)(H2O)(2)(4-C5H4N-COOH)(2)] (1), which was analyzed by single-crystal X-ray diffraction, The complex crystallizes in triclinic space group PY with unit cell parameters: a = 6.337(2), b = 6.894(3), c = 9.178(3). alpha = 99.40(3), beta = 105.26(3), gamma 108.17(5)degrees, V = 354.1(2)Angstrom (3), Z = 1, C12H16CuN2O8, M-r = 379.81, D-c = 1.791 Mg/m(3), F(000) 197, mu (MoK alpha) = 1.589 mm(-1). The final R and wR are 0.068 and 0.170 for 1249 observed reflections with I greater than or equal to2 sigma (I). The central copper ion is in a distorted octahedron geometry completed by two nitrogen atoms from carboxylic ligand, two oxygen atoms from hydroxyl groups and two oxygen atoms from coordinated water molecules. The intermolecular hydrogen bonding leads to the formation of a three-dimensional supramolecular structure.展开更多
基金financially supported by the National Natural Science Foundation of China(No.51373032)
文摘Hydrogen-bonded polymer complex films with the thickness ranging from 50 nm to 2400 nm were prepared by layer-by-layer （LbL） assembly of poly（2-ethyl-2-oxazoline） （PEOX） and poly（acrylic acid） （PAA）. The dewetting behavior of PEOX/PAA films under hydrothermal condition was investigated. It was found that the dewetting occurred at solid-liquid interface, and the typical morphologies such as holes, irregular cellular structure, and droplets were observed. Atomic force microscopy （AFM） revealed the initial rupture of the film. Microscopic Raman and infrared （IR） imaging demonstrated that the PEOX and PAA chains remained association during the dewetting process.
文摘The novel complex{[Co(bipy)(azpy)_(2)(NCS)_(2)]·H_(2)O}n(where bipy=4,4′bipyridine,azpy=4,4′azobisp yridine)has been synthesized and characterized by elemental analyses,IR,UV,thermal analyses,and variable temperature magnetic susceptibility.The crystal(C_(32)H_(26)CoN_(12)OS_(2),Mr=717.70)belongs to the orthorhombic,space group Pnna,a=2.21312(16)nm,b=1.40403(10)nm,c=1.14237(8)nm,V=3.5497(4)nm^(3),Z=4,Dc=1.343g·cm^(-3),μ=0.645mm^(-1),F(000)=1476,and final R_(1)=0.0691,wR_(2)=0.1129 for 231 parameters and 1674 observed reflections[I>2.00σ(I)].The Co(Ⅱ)atom is,in a distorted octahedral geometry,coordinated by six nitrogen atoms from two bridging bipy,two monodentate azpy,and two thiocyanate groups.The bridging ligand bipy links Co(Ⅱ)atoms to form the infinite“rod"with terminal coordination azpy ligand acting as sidearms.Unprecedented three parallel interpenetrating two dimensional(4,4)networks and novel infinite triple helices are formed via hydrogen bonding interactions.CCDC:155588.
基金funding support from the Science Challenge Project(TZ2016004)the National Natural Science Foundation of China(21825601,21790374,21806118,and 21727801)+1 种基金The computational work was financially supported by the Foundation of President of China Academy of Engineering Physics(no.YZJJSQ2017072)by the National Natural Science Foundation of China(21590792,21433005,and 21701006).
文摘Crystalline coordination complexes of actinides,especially in atypical oxidation states,are not only fundamentally important for expanding the notably limited knowledge on the bonding nature of actinides but could also provide critical information toward the development of nuclear fuel cycle,waste management,and national security.Plutonium(Pu)is the only element in the periodic table that could exist in four oxidation states in aqueous solutions simultaneously.
基金The project was supported by the NSF of Liaoning Province (No. 20022018)
文摘A novel complex [Cd2（phen）4（phth）2]·4H2O has been synthesized by the reaction of Hzphth（phthalic acid） and phen（1,10-phenanthroline） with Cd（Ⅱ） in ethanol-water solution. X-ray crystal structure analysis shows it crystallizes in triclinic, space group PI- with a = 10.619（3）, b = 12.560（4）, c = 12.651（4） A, a = 98.775（5）, β = 109.035（5）,γ = 113-576（5）°, C32H24CdN4O6, Mr= 672.95, V = 1381.7（7）A^3, Rint = 0.0358, Z = 2, Dc= 1.618 g/cm^3,μ = 0.845 mm^-1, -6 ≤h≤13, -15 ≤k ≤13, -15 ≤l≤14, F（000） = 680, S = 1.038, R = 0.0480 and wR = 0.0849 for 3992 observed reflections （1 〉 2σ（Ⅰ））. Phth bridges Cd（Ⅱ） to form a macrocyclic compound, and a 2D supramolecular motif is formed through hydrogen bonds and π-π interaction.
基金the National Natural Science Foundation of China (Grant No. 30770587) Program for New Century Excellent Talents in University of China
文摘Previously we successfully prepared poly(vinyldiaminotriazine)(PVDT)-based non-viral vectors which complexed plasmid DNA via hydrogen bonding with adenine-thymine base pairs. In this report, surface charges and complex sizes of this system were further examined. The results showed that PVDT-based polymer could cover surface charges of DNA resulting in slightly negative or neutral complexes. It was also found that the complex sizes were governed by two events: the aggregation induced by the insta-bility of neutral particles, and more compact complexes produced by PVDT-based polymers. In the study of cellular uptake, chlorpromazine and filipin Ⅲ were used to inhibit clathrin- and caveolae-me- diated endocytosis, respectively. We found that PVDT-based systems were transported into cells via a non-clathrin, non-caveolae mediated endocytosis. This special process was studied by temperature inhibition and kinetics assays. It was revealed that such a pathway was characterized by (i) a more en-ergy dependent process and (ii) a much slow transfection-effective internalization.
文摘A novel mixed oxamate copper(Ⅱ) complex \[Cu(phen)(om)(H 2O)\]·H 2O has been obtained and its structure was determined. The complex crystallizes in monoclinic, space group P2(1)/n, a= 0.845 3(0) nm, b=0.971 2(1) nm, c=1.742(1) nm, β=103.89(3)°, V=1.388(0) nm 3, Z=4, R=0.045 8. The copper atom is five-coordinated with a tetragonal pyramid geometry, the complex molecules are linked to form a one-dimensional network via hydrogen bonding. Its X-band EPR spectrum shows an unsymmetric broad signal with g-tensor value 2.12. The IR, TGA and DTA results are also reported. Thermal degradation of the complex starts at 50 ℃ to loss water.
基金Sponsored bythe National Natural Science Foundation of China (20331010 , 20201007 and 90406002) Specialized Research Fund for theDoctoral Programof Higher Education (20030007014)
文摘The single crystal of bi（8-hydroxyquinoline） bihydrated cobalt （Ⅱ） complex, [ Co（Q）2 （H2O2 ] （Q = 8-hydroxyquinoline ion）, has been synthesized by general method and structurally characterized by single crystal X-ray diffraction. Crystal data： C18H16CoN2O4, monoclinic, C2/c, α = 1.336 2（4） nm, b = 0.941 2（3） nm, c = 1.354 3（4） nm, β= 109.672（4）°, Z = 4. In the complex, Co（ Ⅱ ） ion is six-coordinated, forming a distorted octahedron. H-bonding and π-π stacking interaction play a significant role to form and stabilize the three-dimensional structure.
文摘The electronic structures of several dinuclears and trinuclears of molybdenum containing thiolates complexes have been calculated by quantum chemistry SCC-DV-Xa method, and the reactivity of complexes has been analyzed in terms of the molecular orbital energy level diagrams, orbital characters and charge populations.
基金Supported by the Funding Project for Academic Human Resources Development in Institutions of Higher Learning Under the Jurisdiction of Beijing Municipality
文摘A new La（Ⅲ） complex, {[La（L）（NO3）（H2O）3]·H2O}n （L = 1,10-phenanthroline- 2,9-dicarboxylate）, has been synthesized and structurally determined by X-ray diffraction analysis. The complex crystallizes in the monoclinic system, space group P21/c with a = 7.7358（17）, b = 8.1664（18）, c = 28.271（6） A, β= 95.184（4）°, V= 1778.6（7） A3, Z = 4, C14H14LaN3O11, Mr = 539.19, Dc = 2.014 g/cm^3, μ= 2.471 mm^-1, F（000） = 1056, the final R = 0.0350 and wR = 0.0659. In this complex, each metal center adopts a ten-coordination geometry formed by two N atoms from a ligand L and eight O atoms from three H2O molecules, a nitrate ion and carboxylates of two ligands. Each ligand adopts a N2,O3-pentdentate coordination mode using two N and two O atoms chelating a La（Ⅲ）, and using another O atom of carboxylate to bridge another La（Ⅲ） center resulting in a 1D helical chain molecule. Intermolecular strong O-H…O and weak C-H…O hydrogen bonds extend the 1D chain structure into a 3D supramolecular architecture.
基金supported by the National Natural Science Foundation of China(No.21171075)Start-up Fund for Advanced Professional of Jiangsu University(No.08JDG031)
文摘The reactions of imidazoquinoxaline and 1,3,5-H3 btc acid under different condition have been investigated. The different degree of hydrolysis reaction leads to two different adducts being produced, namely, [（Hdiam Quin）＋（H2btc）-]（1）, and [（diam Quin）4（Imi Quin）·4H2O]（2）. Both compounds were characterized by X-ray crystallography. Crystal data for 1： monoclinic, space group Pn with a = 9.868（2）, b = 5.3172（11）, c = 15.387（3）A, β = 91.10（3）°, C17H14N4O6, Mr = 370.32, V = 807.2（3）A3, Z = 2, Dc = 1.524 g/cm3, μ（Mo Kα） = 0.118 mm-1, F（000） = 384, the final R = 0.0385 and w R = 0.0869 for 2294 observed reflections（I 〉 2σ（I））. Crystal data for 2： triclinic, space group P1 with a = 9.825（2）, b = 14.144（3）, c = 16.054（3） A, α = 101.06（3）, β = 102.55（3）, γ = 92.46（3）°, C（44）H40N（20）O4, Mr = 912.96, V = 2128.8（7） A3, Z = 2, Dc = 1.424 g/cm3, μ（Mo Kα） = 0.099 mm-1, F（000） = 952, the final R = 0.0554 and w R = 0.1662 for 6563 observed reflections（I 〉 2σ（I））. X-ray diffraction analysis reveals that compound 1 is a salt. Imidazoquinoxaline was wholly hydrolyzed into 2,3-diaminoquinoxaline and protonated as a cation with H2btc-acting as an anion. However, in compound 2, the imidazoquinoxaline is only partly hydrolyzed, and the resulting 2,3-diaminoquinoxaline forms adduct with the intacted imidazoquinoxaline. Both are further aggregated into 3D frameworks by strong hydrogen bonding even π-π interactions.
基金Project supported by the National Natural Science Foundation of China
文摘The metal alkoxides are very important in the following two respects: (ⅰ) In contrary with the ordinary pi-acceptor ligands which can stabilize metal ions in low oxidation states, the alkoxide ligands can stabilize d-electron poor metals in high oxidation state. Steric control of coordination number of the central metal ion and the binding sites with
基金Supported by the International Scientific and Technological Cooperation Projects of Shanxi Province (2011081022)International S&T Cooperation Program of China (2011DFA51980)
文摘The complex [Tm（TBTA）1.5（bipy）（H2O）2]n （H2TBTA = 2,3,5,6-tetrabromoterephthalic acid, bipy = 2,2-bipyridyl） has been synthesized in water-methanol solution at ambient temperature and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum and thermogravimetric analysis. The crystal belongs to triclinic, space group P1 with a = 11.1429（2）, b = 11.485（2）, c = 12.872（2）, V = 1498.1（5）3 , Z = 2, C22H14Br6N2O9Tm, Mr = 1098.74, Dc = 2.436 g/cm3 , μ（MoKα） = 11.013 mm-1 , F（000） = 1022, T = 296.15 K, the final R （I 〉2σ（I）） = 0.0494 and wR （all data） = 0.1246. The asymmetric unit of the complex is composed of one Tm ion, one and a half of coordinated TBTA 2-anions, one bipy, two coordinated and one lattice water molecules. The adjacent metal ions are bridged by TBTA 2- anions to form a 2D wave-like layer.
文摘A coordination polymer of [Zn(BBP)(p-CPOA)]n (where BBP is 2,6-bis(benzimidazolyl)pyridine and p-CPOA is p-carboxylato-phenoxyacetate dianion) has been synthesized and characterized by elemental analysis,IR,TG,and the single crystal structure was determined by X-ray diffraction. The crystal crystallizes in the monoclinic system,space group of P21/n with a=1.397 3(4) nm,b=1.138 4(3) nm,c=1.575 9(5) nm,β=91.805(1)°,V=2.505 4(13) nm3,Z=4,Dc=1.513 g·cm-3,μ=1.030 mm-1 and F(000)=1 168. Zn(Ⅱ) ion is penta-coordinated and surrounded by two carboxylate O atoms from two different p-CPOA groups in a bis-monodentate mode,three N atoms from the 2,6-bis(benzimidazolyl)pyridine ligand,completing a distorted trigonal bipyramidal coordination configuration. The structure is a helix with a long pitch of 1.138 4 nm. Under direction of supramolecular recognition and attraction,the adjacent chains are formed the double-stranded chain through π-π stacking between the 2,6-bis(benzimidazolyl)pyridine ligands and hydrogen-bonding interactions. A three-dimensional supramolecular network is further constructed through these interactions between the helices. The TG shows that its chain skeleton is thermally stable up to 382 ℃.
基金supported by the National Natural Science Foundation of China(No.21688102,No.21573047and No.21273045)
文摘Binuclear transition metal carbonyl clusters serve as the simplest models in understand- ing metal-metal and ligand bonding that are important organometallic chemistry catalysis. Binuclear first row transition metal carbonyl ions are produced via a pulsed laser vaporiza- tion/supersonic expansion cluster ion source in the gas phase. These ions are studied by mass-selected infrared photodissociation spectroscopy in the carbonyl stretching frequency region. Density functional theory calculations have been performed on the geometric struc- tures and vibrational spectra of the carbonyl ions. Their geometric and electronic structures are determined by comparison of the experimental IR spectra with the simulated spectra. The structure and the metM-metal and metal-CO bonding of both saturated and unsaturated homonuclear as well as heteronuclear carbonyl cluster cations and anions are discussed.
文摘The hydrothermal reaction of isonicotinic acid (4-C5H4N-COOH), Cu(ClO4)(2). 6H(2)O and water at 170 degreesC gave the title compound, [Cu(OH)(2)(H2O)(2)(4-C5H4N-COOH)(2)] (1), which was analyzed by single-crystal X-ray diffraction, The complex crystallizes in triclinic space group PY with unit cell parameters: a = 6.337(2), b = 6.894(3), c = 9.178(3). alpha = 99.40(3), beta = 105.26(3), gamma 108.17(5)degrees, V = 354.1(2)Angstrom (3), Z = 1, C12H16CuN2O8, M-r = 379.81, D-c = 1.791 Mg/m(3), F(000) 197, mu (MoK alpha) = 1.589 mm(-1). The final R and wR are 0.068 and 0.170 for 1249 observed reflections with I greater than or equal to2 sigma (I). The central copper ion is in a distorted octahedron geometry completed by two nitrogen atoms from carboxylic ligand, two oxygen atoms from hydroxyl groups and two oxygen atoms from coordinated water molecules. The intermolecular hydrogen bonding leads to the formation of a three-dimensional supramolecular structure.
