The novel complex {[Co(bipy)(azpy)2(NCS)2]· H2O}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 tem...The novel complex {[Co(bipy)(azpy)2(NCS)2]· H2O}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 (C32H26CoN12OS2, 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)nm3, Z=4, Dc=1.343g· cm- 3, μ =0.645mm- 1, F(000)=1476, and final R1=0.0691, wR2=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
Two new organic supramolecular cocrystal complexes C18H18O4·C10H8N2（I） and C18H18O4·C12H10N2（II）（C18H18O4 = 2,3,6,7-tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene（LH4）, C10H8N2 = 4,4＇...Two new organic supramolecular cocrystal complexes C18H18O4·C10H8N2（I） and C18H18O4·C12H10N2（II）（C18H18O4 = 2,3,6,7-tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene（LH4）, C10H8N2 = 4,4＇-bipyridine（bpy） and C12H10N2 = 4,4＇-bipyridinylethane（bpe）） have been obtained by mixing LH4 with corresponding bpy or bpe ligand. The two complexes have been determined by X-ray crystal structure analysis, elemental analysis and IR analysis. Compound I crystallizes in the orthorhombic Pnma with a = 9.7078（4）, b = 22.4974（10）, c = 20.6272（9） V = 4505.0（3）3, Mr = 454.51, Dc. = 1.340 g·cm^-3, μ = 0.09 mm-1, F（000） = 1920, Z = 8, R = 0.0503 and wR = 0.1360. Compound II crystallizes in monoclinic C2/c with a = 29.944（6）, b = 9.820（2）, c = 22.643（5） , V = 5048.4（18）3, Mr = 480.54, Dc. = 1.265 g cm^–3, μ = 0.084 mm^–1, F（000） = 2032, Z = 8, R = 0.0548 and wR = 0.1600. X-ray single-crystal structure analysis shows that two-dimensional（2D） layer supramolecular structures are formed through hydrogen bonds and π-π interactions in the two complexes. IR analysis also indicates that there are only associated hydroxyl groups in the two complexes.展开更多
A new 3D metal-organic framework of {[Co3（IDC）2（bipy）2（py）2]·7H2O}n （1） was obtained by the hydrothermal reaction of Co（NO3）2·6H2O, imidazole-4,5-dicarboxylic acid （H3IDC）, 4,4＇-bipyridine （bip...A new 3D metal-organic framework of {[Co3（IDC）2（bipy）2（py）2]·7H2O}n （1） was obtained by the hydrothermal reaction of Co（NO3）2·6H2O, imidazole-4,5-dicarboxylic acid （H3IDC）, 4,4＇-bipyridine （bipy）, and pyridine （py）, and structurally characterized by elemental analysis, infrared spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction crystal structural analysis reveals that it crystallizes in orthorhombic system, space group Pccn with a = 11.1040（3）, b = 19.8834（5）, c = 21.3025（5）, V = 4703.3（2）3, Mr = 1079.63, Z = 4, Dc = 1.525 Mg·m-3, F（000） = 2212, μ（CuKα） = 8.855 mm-1, the final R = 0.0331 and wR = 0.0713 for 2525 observed reflections with I ≥ 2σ（I）. In compound 1, each cobalt（II） ion is six-coordinated with a slightly distorted octahedral coordination geometry, and each μ3-IDC3- acts as a bridge to bond three neighboring Co（II） ions, leading to an infinite 2D network layer structure of [Co3（IDC）2]n with Kagomé lattice. The adjacent layers are further linked by μ2-bipy to form an infinite 3D layered-pillared framework architecture of [Co3（IDC）2（bipy）2（py）2]n.展开更多
Co-crystallization of pztcH_4 with 4,4＇-bipyridine（4,4＇-bipy） in pH = 3-4 and 1-2 gave two new binary molecular adducts： [（4,4＇-bipy H2）（pztc H2）]（1） and [（4,4＇-bipy H2）（pztcH3）（Cl）]·4H2O（2）,...Co-crystallization of pztcH_4 with 4,4＇-bipyridine（4,4＇-bipy） in pH = 3-4 and 1-2 gave two new binary molecular adducts： [（4,4＇-bipy H2）（pztc H2）]（1） and [（4,4＇-bipy H2）（pztcH3）（Cl）]·4H2O（2）, respectively. Compounds 1 and 2 have been characterized by IR, elemental analysis, NMR and X-ray single-crystal diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 5.7752（12）, b = 7.9126（16）, c = 9.4492（19） ？, α = 97.49（3）, β = 107.71（3）, γ = 94.52（3）o, V = 404.62（14） A^3, Z = 1, μ = 0.137 mm^1, Dc = 1.692 Mg/m^3, C18H12N4O8, Mr = 412.32, F（000） = 212, S = 1.025, R = 0.0360 and wR = 0.0973. Compound 2 crystallizes in monoclinic, space group C2/c with a = 17.093（3）, b = 7.7665（16）, c = 18.414（4） A, β = 113.36（3）o, V = 2244.1（8） A^3, Z = 4, μ = 0.244 mm^-1, Dc = 1.542 Mg/m^3, C18H21ClN4O12, Mr = 520.84, F（000） = 1080, S = 1.021, R = 0.0343 and wR = 0.0978. In compound 1, pztc H22- anions self-formed 2-D sheets by strong Oacid-H···Oacidhydrogen bonds, which are further extended to form a 3-D supramolecular network bridged with 4,4？-bipy via N-H···Oacid interactions. In compound 2, besides the 1-D chain constructed by pztc H3-itself through strong H-bond Oacid-H···Oacid, the other chain is constructed with 4,4？-bipy H22＋, Cl-anion and water molecules by moderate H-bonds and Ow-H···Cl and N-H···Ow. The two chains are linked with μ3-connected water molecules resulting from the combination of strong synthon-assisted H-bonding Oacid-H···Ow to afford an interlaced 3-D network.展开更多
By using solvothermal method, two new metal coordination polymers based on 2,5-furandicarboxylic acid（H2FDA） ligand and 4,4＇-bipyridine（bipy）, [Cu（FDA）（4,4＇-bipy）（DMF）]n·solvent（1） and {[Zn（4,4＇-b...By using solvothermal method, two new metal coordination polymers based on 2,5-furandicarboxylic acid（H2FDA） ligand and 4,4＇-bipyridine（bipy）, [Cu（FDA）（4,4＇-bipy）（DMF）]n·solvent（1） and {[Zn（4,4＇-bipy）（FDA）（DMF）]·DMF}n（2）, were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR and powder X-ray diffraction. Compound 1 crystallizes in monoclinic space group P21/c with a = 11.104（2）, b = 10.396（2）, c = 18.772（4） , β = 96.20（3）o, V = 2154.2（7） 3, Dc = 1.378 g/cm^3, C19H17 Cu N3O6, Mr = 446.90, F（000） = 916, μ（Mo Kα） = 1.05 mm^-1, Z = 4, R = 0.0691 and wR = 0.1341 for 3537 observed reflections（I 2σ（I））, and R = 0.1062 and w R = 0.1482 for all data. Compound 2 crystallizes in monoclinic space group C2/c with a = 29.779（6）, b = 9.6417（19）, c = 17.292（3）, β = 105.69（3）°, V = 4779.9（16） 3, Dc = 1.445 g/cm^3, C22H22N4O7 Zn, Mr = 519.81, F（000） = 2144, μ（Mo Kα）= 1.08 mm^-1, Z = 8, R = 0.0641 and w R = 0.1007 for 2985 observed reflections（I 2σ（I））, and R = 0.1028 and w R = 0.1112 for all data. Different coordination geometry of metal ions, square pyramid of Cu2＋ and trigonal bipyramid of Zn2＋, bring about different orientations of FDA2- ligands as well as 4,4＇-bipyridine ligands, and furthermore distinct assembly structures for 1 and 2. The thermal stabilities of 1 and 2 are also investigated.展开更多
Fourier-transform infrared（FTIR）,Raman and ultraviolet-visible spectra of 4,4＇-bipyridine and its me-tal-organic coordination compounds synthesized from 4,4＇-bipyridine and nitrate of Co（Ⅱ）,Ni（Ⅱ） and Zn（Ⅱ...Fourier-transform infrared（FTIR）,Raman and ultraviolet-visible spectra of 4,4＇-bipyridine and its me-tal-organic coordination compounds synthesized from 4,4＇-bipyridine and nitrate of Co（Ⅱ）,Ni（Ⅱ） and Zn（Ⅱ） were measured and analyzed,respectively.The main FTIR and Raman bands were assigned in detail.The relationship between these characteristic bands and the structure of ligands and coordination compounds were discussed.展开更多
Recently,azobenzene-4,4'-dicarboxylic acid(ADCA)has been produced gradually for use as an organic synthesis or pharmaceutical intermediate due to its eminent performance.With large quantities put into application ...Recently,azobenzene-4,4'-dicarboxylic acid(ADCA)has been produced gradually for use as an organic synthesis or pharmaceutical intermediate due to its eminent performance.With large quantities put into application in the future,the thermal stability of this substance during storage,transportation,and use will become quite important.Thus,in this work,the thermal decomposition behavior,thermal decomposition kinetics,and thermal hazard of ADCA were investigated.Experiments were conducted by using a SENSYS evo DSC device.A combination of differential iso-conversion method,compensation parameter method,and nonlinear fitting evaluation were also used to analyze thermal kinetics and mechanism of ADCA decomposition.The results show that when conversion rate α increases,the activation energies of ADCA's first and main decomposition peaks fall.The amount of heat released during decomposition varies between 182.46 and 231.16 J·g^(-1).The proposed kinetic equation is based on the Avrami-Erofeev model,which is consistent with the decomposition progress.Applying the Frank-Kamenetskii model,a calculated self-accelerating decomposition temperature of 287.0℃is obtained.展开更多
文摘The novel complex {[Co(bipy)(azpy)2(NCS)2]· H2O}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 (C32H26CoN12OS2, 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)nm3, Z=4, Dc=1.343g· cm- 3, μ =0.645mm- 1, F(000)=1476, and final R1=0.0691, wR2=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supported by the National Natural Science Foundation of China(No.21176246)Jiangsu Qinglan Project
文摘Two new organic supramolecular cocrystal complexes C18H18O4·C10H8N2（I） and C18H18O4·C12H10N2（II）（C18H18O4 = 2,3,6,7-tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene（LH4）, C10H8N2 = 4,4＇-bipyridine（bpy） and C12H10N2 = 4,4＇-bipyridinylethane（bpe）） have been obtained by mixing LH4 with corresponding bpy or bpe ligand. The two complexes have been determined by X-ray crystal structure analysis, elemental analysis and IR analysis. Compound I crystallizes in the orthorhombic Pnma with a = 9.7078（4）, b = 22.4974（10）, c = 20.6272（9） V = 4505.0（3）3, Mr = 454.51, Dc. = 1.340 g·cm^-3, μ = 0.09 mm-1, F（000） = 1920, Z = 8, R = 0.0503 and wR = 0.1360. Compound II crystallizes in monoclinic C2/c with a = 29.944（6）, b = 9.820（2）, c = 22.643（5） , V = 5048.4（18）3, Mr = 480.54, Dc. = 1.265 g cm^–3, μ = 0.084 mm^–1, F（000） = 2032, Z = 8, R = 0.0548 and wR = 0.1600. X-ray single-crystal structure analysis shows that two-dimensional（2D） layer supramolecular structures are formed through hydrogen bonds and π-π interactions in the two complexes. IR analysis also indicates that there are only associated hydroxyl groups in the two complexes.
基金supported by the National Natural Science Foundation of China (No. 21071099)
文摘A new 3D metal-organic framework of {[Co3（IDC）2（bipy）2（py）2]·7H2O}n （1） was obtained by the hydrothermal reaction of Co（NO3）2·6H2O, imidazole-4,5-dicarboxylic acid （H3IDC）, 4,4＇-bipyridine （bipy）, and pyridine （py）, and structurally characterized by elemental analysis, infrared spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction crystal structural analysis reveals that it crystallizes in orthorhombic system, space group Pccn with a = 11.1040（3）, b = 19.8834（5）, c = 21.3025（5）, V = 4703.3（2）3, Mr = 1079.63, Z = 4, Dc = 1.525 Mg·m-3, F（000） = 2212, μ（CuKα） = 8.855 mm-1, the final R = 0.0331 and wR = 0.0713 for 2525 observed reflections with I ≥ 2σ（I）. In compound 1, each cobalt（II） ion is six-coordinated with a slightly distorted octahedral coordination geometry, and each μ3-IDC3- acts as a bridge to bond three neighboring Co（II） ions, leading to an infinite 2D network layer structure of [Co3（IDC）2]n with Kagomé lattice. The adjacent layers are further linked by μ2-bipy to form an infinite 3D layered-pillared framework architecture of [Co3（IDC）2（bipy）2（py）2]n.
基金supported by the National Natural Science Foundation of China(No.21571094)
文摘Co-crystallization of pztcH_4 with 4,4＇-bipyridine（4,4＇-bipy） in pH = 3-4 and 1-2 gave two new binary molecular adducts： [（4,4＇-bipy H2）（pztc H2）]（1） and [（4,4＇-bipy H2）（pztcH3）（Cl）]·4H2O（2）, respectively. Compounds 1 and 2 have been characterized by IR, elemental analysis, NMR and X-ray single-crystal diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 5.7752（12）, b = 7.9126（16）, c = 9.4492（19） ？, α = 97.49（3）, β = 107.71（3）, γ = 94.52（3）o, V = 404.62（14） A^3, Z = 1, μ = 0.137 mm^1, Dc = 1.692 Mg/m^3, C18H12N4O8, Mr = 412.32, F（000） = 212, S = 1.025, R = 0.0360 and wR = 0.0973. Compound 2 crystallizes in monoclinic, space group C2/c with a = 17.093（3）, b = 7.7665（16）, c = 18.414（4） A, β = 113.36（3）o, V = 2244.1（8） A^3, Z = 4, μ = 0.244 mm^-1, Dc = 1.542 Mg/m^3, C18H21ClN4O12, Mr = 520.84, F（000） = 1080, S = 1.021, R = 0.0343 and wR = 0.0978. In compound 1, pztc H22- anions self-formed 2-D sheets by strong Oacid-H···Oacidhydrogen bonds, which are further extended to form a 3-D supramolecular network bridged with 4,4？-bipy via N-H···Oacid interactions. In compound 2, besides the 1-D chain constructed by pztc H3-itself through strong H-bond Oacid-H···Oacid, the other chain is constructed with 4,4？-bipy H22＋, Cl-anion and water molecules by moderate H-bonds and Ow-H···Cl and N-H···Ow. The two chains are linked with μ3-connected water molecules resulting from the combination of strong synthon-assisted H-bonding Oacid-H···Ow to afford an interlaced 3-D network.
基金supported by URT program of Beijing Institute of Petrochemical Technology(Beijing municipal level 2015J00058)URT program of Beijing Institute of Petrochemical Technology(State level 2015J00056)
文摘By using solvothermal method, two new metal coordination polymers based on 2,5-furandicarboxylic acid（H2FDA） ligand and 4,4＇-bipyridine（bipy）, [Cu（FDA）（4,4＇-bipy）（DMF）]n·solvent（1） and {[Zn（4,4＇-bipy）（FDA）（DMF）]·DMF}n（2）, were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR and powder X-ray diffraction. Compound 1 crystallizes in monoclinic space group P21/c with a = 11.104（2）, b = 10.396（2）, c = 18.772（4） , β = 96.20（3）o, V = 2154.2（7） 3, Dc = 1.378 g/cm^3, C19H17 Cu N3O6, Mr = 446.90, F（000） = 916, μ（Mo Kα） = 1.05 mm^-1, Z = 4, R = 0.0691 and wR = 0.1341 for 3537 observed reflections（I 2σ（I））, and R = 0.1062 and w R = 0.1482 for all data. Compound 2 crystallizes in monoclinic space group C2/c with a = 29.779（6）, b = 9.6417（19）, c = 17.292（3）, β = 105.69（3）°, V = 4779.9（16） 3, Dc = 1.445 g/cm^3, C22H22N4O7 Zn, Mr = 519.81, F（000） = 2144, μ（Mo Kα）= 1.08 mm^-1, Z = 8, R = 0.0641 and w R = 0.1007 for 2985 observed reflections（I 2σ（I））, and R = 0.1028 and w R = 0.1112 for all data. Different coordination geometry of metal ions, square pyramid of Cu2＋ and trigonal bipyramid of Zn2＋, bring about different orientations of FDA2- ligands as well as 4,4＇-bipyridine ligands, and furthermore distinct assembly structures for 1 and 2. The thermal stabilities of 1 and 2 are also investigated.
基金Supported by the National Natural Science Foundation of China(Nos.20773044,20873050,20921003 and 20973074)the "111" Project of Minstry of Education of China(No.B06009)
文摘Fourier-transform infrared（FTIR）,Raman and ultraviolet-visible spectra of 4,4＇-bipyridine and its me-tal-organic coordination compounds synthesized from 4,4＇-bipyridine and nitrate of Co（Ⅱ）,Ni（Ⅱ） and Zn（Ⅱ） were measured and analyzed,respectively.The main FTIR and Raman bands were assigned in detail.The relationship between these characteristic bands and the structure of ligands and coordination compounds were discussed.
基金supported by National Natural Science Foundation of China(51974166).
文摘Recently,azobenzene-4,4'-dicarboxylic acid(ADCA)has been produced gradually for use as an organic synthesis or pharmaceutical intermediate due to its eminent performance.With large quantities put into application in the future,the thermal stability of this substance during storage,transportation,and use will become quite important.Thus,in this work,the thermal decomposition behavior,thermal decomposition kinetics,and thermal hazard of ADCA were investigated.Experiments were conducted by using a SENSYS evo DSC device.A combination of differential iso-conversion method,compensation parameter method,and nonlinear fitting evaluation were also used to analyze thermal kinetics and mechanism of ADCA decomposition.The results show that when conversion rate α increases,the activation energies of ADCA's first and main decomposition peaks fall.The amount of heat released during decomposition varies between 182.46 and 231.16 J·g^(-1).The proposed kinetic equation is based on the Avrami-Erofeev model,which is consistent with the decomposition progress.Applying the Frank-Kamenetskii model,a calculated self-accelerating decomposition temperature of 287.0℃is obtained.
