Hydroxylation of inert benzene through the activation of the C_(sp2)-H bond is a representative reaction about the transformation of C-H bonds to C-O bonds,which has far-reaching guiding significance but remains a cha...Hydroxylation of inert benzene through the activation of the C_(sp2)-H bond is a representative reaction about the transformation of C-H bonds to C-O bonds,which has far-reaching guiding significance but remains a challenging scientific problem.To overcome this problem,a series of VOx-Ga_(2)O_(3)/SiO_(2)-Al_(2)O_(3)were prepared to achieve an efficient and economical hydroxylation path of benzene to phenol.The results showed that the phenol yield was 72.89%(selectivity>98.1%)under the optimum conditions.The reason is that the C-H bond in the benzene ring is activated by heterolysis over a VOx-Ga_(2)O_(3)/SiO_(2)-Al_(2)O_(3)catalyst.Meanwhile,the introduction of aluminum(Al)and gallium(Ga)made a qualitative change in the catalyst,enhancing the electron motion and spin motion of vanadium species,resulting in the increase of V4^(+)/V5^(+)ratio.In addition,the catalyst can provide an optimal acidic environment and a threedimensional cross-linked surface structure that facilitates product diffusion.展开更多
Results of oxidation 2-(N-acetylamine)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid oxygen depend on temperature. At 55℃?- 60℃, 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa i...Results of oxidation 2-(N-acetylamine)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid oxygen depend on temperature. At 55℃?- 60℃, 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa is formed. The constitution is based on dates of spectrums 1Н and 13С NMR. At 95℃?- 97℃, mixtures of 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa and of 6,8-di-tert-butyl-3-(N-acetylamine)spiro(4,5)deca-1-oxa-5,8-dien-2,7-dione are produced. Structures are calculated by the method of Hartrii-Foka. Values of enthalpies and of entropies allow to assume dynamic isomerism.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
Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terp...Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.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
A new coordination polymer {[Cd（C_（21）H_（14）N_6）（C_8H_4O_4）]·H_2O}_n（1） was synthesized by an elaborate design via the reaction of 3-（2,6-di（pyrazin-2-yl）pyridin-4-yl）-1H-indole（bppi）,1,4-benzene-...A new coordination polymer {[Cd（C_（21）H_（14）N_6）（C_8H_4O_4）]·H_2O}_n（1） was synthesized by an elaborate design via the reaction of 3-（2,6-di（pyrazin-2-yl）pyridin-4-yl）-1H-indole（bppi）,1,4-benzene-dicarboxylic acid（H2bdc） and cadmium（Ⅱ） nitrate in CH_3OH/H_2O mixed solvents. Complex 1 crystallizes in orthorhombic,space group Ccca with a = 20.012（4）,b = 31.881（6）,c = 19.808（4） ？,V = 12638（4） ？~3,Z = 16,C_（29）H_（20）CdN_6O_5,M_r = 644.91,D_c = 1.356 g·cm^（-3）,μ = 0.735 mm^（-1）,F（000） = 5184,GOOF = 1.046,the final R = 0.0405 and wR = 0.1063 for 6870 observed reflections（I 〉 2σ（I））. The Cd（Ⅱ） centre is hepta-coordinated by three N and four O atoms from one bppi terminal ligand and two bdc2– ligands,respectively,displaying a capped trigonal prism geometry. Structure extension gives coordination polymeric chains,in which the bdc2– linkers connect Cd（Ⅱ） cations into a one-dimensional（1D） coordination polymer along the c axis,giving zigzag chains with the Cd···Cd separation of 11.178（1） ？. The adjacent bppi terminal ligands in the chains are anti-periplanar conformation. The three-dimensional（3D） structure is stabilized by π···π stacking and hydrogen-bonding interactions to form a supramolecular self-penetrating network with 1D channels. In 1,there are voids 2999.7 ？~3 with 23.7% of per unit cell volume. Thermal analysis indicates that the framework of 1 is stable until 651 K and the photoluminescence of 1 in the solid shows very weak fluorescence at 382 and 560 nm upon excitation at 310 nm.展开更多
基金the Support Program for Hongliu Young Teachers of Lanzhou University of Technology(02/062214)Young Talent Innovation Project of Lanzhou(2023-QN-103)Major science and technology projects of Gansu Province(22ZD6GA013).
文摘Hydroxylation of inert benzene through the activation of the C_(sp2)-H bond is a representative reaction about the transformation of C-H bonds to C-O bonds,which has far-reaching guiding significance but remains a challenging scientific problem.To overcome this problem,a series of VOx-Ga_(2)O_(3)/SiO_(2)-Al_(2)O_(3)were prepared to achieve an efficient and economical hydroxylation path of benzene to phenol.The results showed that the phenol yield was 72.89%(selectivity>98.1%)under the optimum conditions.The reason is that the C-H bond in the benzene ring is activated by heterolysis over a VOx-Ga_(2)O_(3)/SiO_(2)-Al_(2)O_(3)catalyst.Meanwhile,the introduction of aluminum(Al)and gallium(Ga)made a qualitative change in the catalyst,enhancing the electron motion and spin motion of vanadium species,resulting in the increase of V4^(+)/V5^(+)ratio.In addition,the catalyst can provide an optimal acidic environment and a threedimensional cross-linked surface structure that facilitates product diffusion.
文摘Results of oxidation 2-(N-acetylamine)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid oxygen depend on temperature. At 55℃?- 60℃, 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa is formed. The constitution is based on dates of spectrums 1Н and 13С NMR. At 95℃?- 97℃, mixtures of 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa and of 6,8-di-tert-butyl-3-(N-acetylamine)spiro(4,5)deca-1-oxa-5,8-dien-2,7-dione are produced. Structures are calculated by the method of Hartrii-Foka. Values of enthalpies and of entropies allow to assume dynamic isomerism.
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 Program for New Century Excellent Talents in University(NCET-10-0176)the Natural Science Foundation of Jilin Province(No.20130521019JH)the fund of Jilin Provincial Education Department of China(No.2014154)
文摘Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.
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 the National Natural Science Foundation of China(Nos.21571118&21271121)
文摘A new coordination polymer {[Cd（C_（21）H_（14）N_6）（C_8H_4O_4）]·H_2O}_n（1） was synthesized by an elaborate design via the reaction of 3-（2,6-di（pyrazin-2-yl）pyridin-4-yl）-1H-indole（bppi）,1,4-benzene-dicarboxylic acid（H2bdc） and cadmium（Ⅱ） nitrate in CH_3OH/H_2O mixed solvents. Complex 1 crystallizes in orthorhombic,space group Ccca with a = 20.012（4）,b = 31.881（6）,c = 19.808（4） ？,V = 12638（4） ？~3,Z = 16,C_（29）H_（20）CdN_6O_5,M_r = 644.91,D_c = 1.356 g·cm^（-3）,μ = 0.735 mm^（-1）,F（000） = 5184,GOOF = 1.046,the final R = 0.0405 and wR = 0.1063 for 6870 observed reflections（I 〉 2σ（I））. The Cd（Ⅱ） centre is hepta-coordinated by three N and four O atoms from one bppi terminal ligand and two bdc2– ligands,respectively,displaying a capped trigonal prism geometry. Structure extension gives coordination polymeric chains,in which the bdc2– linkers connect Cd（Ⅱ） cations into a one-dimensional（1D） coordination polymer along the c axis,giving zigzag chains with the Cd···Cd separation of 11.178（1） ？. The adjacent bppi terminal ligands in the chains are anti-periplanar conformation. The three-dimensional（3D） structure is stabilized by π···π stacking and hydrogen-bonding interactions to form a supramolecular self-penetrating network with 1D channels. In 1,there are voids 2999.7 ？~3 with 23.7% of per unit cell volume. Thermal analysis indicates that the framework of 1 is stable until 651 K and the photoluminescence of 1 in the solid shows very weak fluorescence at 382 and 560 nm upon excitation at 310 nm.
