The reaction of Mn(OAc)2·4 H2 O, 5-ethyl-pyridine-2,3-dicarboxylic acid(H2 epda) and 4,4?-bipyridine(4,4?-bipy)/4,4?-bis(imidazolyl)biphenyl)(bibp) under hydrothermal conditions produced two new manganese(Ⅱ) MOF...The reaction of Mn(OAc)2·4 H2 O, 5-ethyl-pyridine-2,3-dicarboxylic acid(H2 epda) and 4,4?-bipyridine(4,4?-bipy)/4,4?-bis(imidazolyl)biphenyl)(bibp) under hydrothermal conditions produced two new manganese(Ⅱ) MOFs [Mn(epda)(4,4?-bipy)1/2](1) and [Mn(epda)(bibp)1/2](2), which were characterized by elemental analysis, infrared spectroscopy, thermogravimetric analyses, and single-crystal X-ray diffraction. The structures of complexes 1 and 2 are similar. In 1, the adjacent Mn(Ⅱ) ions are connected by epda dianion to generate a 2 D(4,4) grid layer, and such 2 D layers are further connected via bibp ligand to form another layer, forming a 2 D pillared-layer. Topologically, the Mn atoms as the node are bridged by the edpa anions and bibp ligands to form a uninodal 5-connected network topology. The magnetic properties of 1 and 2 have also been-investigated, and the exchange interctions were –1.39 and –1.05 cm1, respectively. According to the crystal structures, compounds 1 and 2 were carried out by using hybrid DFT methods at the B3 LYP/6-31 G(d) level. The DFT-BS approach was applied to study the magnetic coupling behaviors for 1 and 2. The result reveals that the calculated exchange coupling constants J were in good agreement with the experimental data.展开更多
A three-dimensional(3 D) Cd-based metal-organic framework(MOF), [Cd(H2 O)(PAA)]·(H2 O)2(complex 1) has been rationally designed and synthesized by using 4-(pyrimidin-5-yl)isophthalic acid(H2 PAA) and Cd(NO3)2...A three-dimensional(3 D) Cd-based metal-organic framework(MOF), [Cd(H2 O)(PAA)]·(H2 O)2(complex 1) has been rationally designed and synthesized by using 4-(pyrimidin-5-yl)isophthalic acid(H2 PAA) and Cd(NO3)2·4 H2 O under solvothermal conditions. The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction(PXRD) and thermogravimetric analyses(TGA). Single-crystal X-ray diffraction analyses reveal that complex 1 consists of a 3 D network with one-dimensional(1 D) channels. Moreover, 1 exhibits strong luminescent emission in solid state at room temperature. Fluorescence quenching was observed when treating complex 1 with picric acid(PA), 2,4-dinitrophenylhydrazine(2,4-DNPH) and p-nitroaniline(p-NA), revealing that the as-synthesized complex could be used as a luminescence sensor for the detection of PA, 2,4-DNPH and p-NA.展开更多
A new zinc coordination polymer（CP） {[Zn1.5（ttb）0.5（phen）（H2O）]·2 H2O}n（1）,（H6ttb = 3,4,5-tricarboxyl-（3?,4?,5?-tricarboxylazophenyl）benzene, phen = 1,10-phenanthroline）, has been hydrothermally syn...A new zinc coordination polymer（CP） {[Zn1.5（ttb）0.5（phen）（H2O）]·2 H2O}n（1）,（H6ttb = 3,4,5-tricarboxyl-（3?,4?,5?-tricarboxylazophenyl）benzene, phen = 1,10-phenanthroline）, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray determination, IR and thermogravimetric analysis（TGA）. CP 1 crystallizes in the monoclinic system, space group C2/c with a = 12.402（3）, b = 15.231（3）, c = 22.233（4） ?, β = 94.388（3）°, Zn1.5C21H16N3O9, Mr = 552.42, V = 4187.3（15） ?3, Dc = 1.753 g/cm3, F（000） = 2240, μ = 1.795 mm-1, S = 1.041, GOF = 1.041, Rint = 0.0169, 2.36°<θ<30.95°, and Z = 8. The final refinement gave R = 0.0340 and w R = 0.0927 for 5791 observed reflections with I > 2σ（I）. The completely deprotonated（ttb）6- ion in 1 adopts an octadentate coordination mode（μ8-η2-η1-η1-η1-η1-η2）. Four of the carboxyl groups are coordinated with four zinc ions by monodentate, respectively. While the other two carboxyl groups are coordinated with four zinc ions by bidentate, respectively. So, CP 1 possesses a 3 D network structure cross-linked by（ttb）6-ion. The XRD, UV and photoluminescence properties of CP 1 were also studied. Remarkably, 1 exhibits photocatalytic activities for the degradation of dye（MO） under UV light irradiation and shows good stabilities towards UV-light photocatalysis.展开更多
Two metal-organic frameworks(MOFs) of formulae [Co7(L)3(4,4′-BPy)2(OH)2(H2O)6]·-4 H2O(1) and [Cd2(L)(2,2′-BPy)2]n(2, H4L = 5-(3,5-dicarboxybenzyloxy)-isophthalic acid,2,2′-BPy = 2,2?-bipyridine, 4,4′-BPy = 4,...Two metal-organic frameworks(MOFs) of formulae [Co7(L)3(4,4′-BPy)2(OH)2(H2O)6]·-4 H2O(1) and [Cd2(L)(2,2′-BPy)2]n(2, H4L = 5-(3,5-dicarboxybenzyloxy)-isophthalic acid,2,2′-BPy = 2,2?-bipyridine, 4,4′-BPy = 4,4′-bipyridine) were synthesized under solvothermal conditions. The structures of 1 and 2 were characterized by X-ray single-crystal diffraction analysis.In complex 1, six cobalt atoms were connected by oxygen atoms to form a defect dicubane structure. The defect dicubane structures were further linked by Co(4,4?-BPy) units to generate a3-D network structure. Compound 2 displays a 2-D chain structure. The photoluminescent property of complex 2 is investigated. The results show the exclusive luminescence emission bands being originated from intraligand π-π^* transitions.展开更多
Two new complexes[Co_(2)(L)(4,4´-bip)(H_(2)O)_(3)]_(n)(1)and{[Co(L´)_(2)(phen)]·2H_(2)O)}_(n)(2)(H_(4)L=1-(3,5-dicarboxybenzyl)-3,5-pyrazole dicarboxylic acid,H_(3)L´=1-(3,5-dicarboxybenzyl)-3-pyra...Two new complexes[Co_(2)(L)(4,4´-bip)(H_(2)O)_(3)]_(n)(1)and{[Co(L´)_(2)(phen)]·2H_(2)O)}_(n)(2)(H_(4)L=1-(3,5-dicarboxybenzyl)-3,5-pyrazole dicarboxylic acid,H_(3)L´=1-(3,5-dicarboxybenzyl)-3-pyrazole carboxylic acid,4,4´-bip=4,4´-bis(1-imidazolyl)biphenyl,phen=1,10-phenanthroline)were synthesized.Complexes 1 and 2 have been characterized by IR spectrography,X-ray single-crystal diffraction,elemental analysis and thermogravimetry.1 crystallizes in monoclinic system,space group P2_(1/c).Complex 2 crystallizes in monoclinic system,space group I2/a.It is remarkable that in situ hydrothermal decarboxylation was observed during preparing complex 2.In addition,magnetic analysis indicates that antiferromagnetic interaction exists among Co(Ⅱ)ions in complexes 1 and 2.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21573189,21503183 and 21763028)the National College Students’innovation and entrepreneurship training program(D2018)
文摘The reaction of Mn(OAc)2·4 H2 O, 5-ethyl-pyridine-2,3-dicarboxylic acid(H2 epda) and 4,4?-bipyridine(4,4?-bipy)/4,4?-bis(imidazolyl)biphenyl)(bibp) under hydrothermal conditions produced two new manganese(Ⅱ) MOFs [Mn(epda)(4,4?-bipy)1/2](1) and [Mn(epda)(bibp)1/2](2), which were characterized by elemental analysis, infrared spectroscopy, thermogravimetric analyses, and single-crystal X-ray diffraction. The structures of complexes 1 and 2 are similar. In 1, the adjacent Mn(Ⅱ) ions are connected by epda dianion to generate a 2 D(4,4) grid layer, and such 2 D layers are further connected via bibp ligand to form another layer, forming a 2 D pillared-layer. Topologically, the Mn atoms as the node are bridged by the edpa anions and bibp ligands to form a uninodal 5-connected network topology. The magnetic properties of 1 and 2 have also been-investigated, and the exchange interctions were –1.39 and –1.05 cm1, respectively. According to the crystal structures, compounds 1 and 2 were carried out by using hybrid DFT methods at the B3 LYP/6-31 G(d) level. The DFT-BS approach was applied to study the magnetic coupling behaviors for 1 and 2. The result reveals that the calculated exchange coupling constants J were in good agreement with the experimental data.
基金supported by the Natural Science Foundation of Shaanxi Province(2018JQ2079,2018JQ2040,2018JM2055)
文摘A three-dimensional(3 D) Cd-based metal-organic framework(MOF), [Cd(H2 O)(PAA)]·(H2 O)2(complex 1) has been rationally designed and synthesized by using 4-(pyrimidin-5-yl)isophthalic acid(H2 PAA) and Cd(NO3)2·4 H2 O under solvothermal conditions. The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction(PXRD) and thermogravimetric analyses(TGA). Single-crystal X-ray diffraction analyses reveal that complex 1 consists of a 3 D network with one-dimensional(1 D) channels. Moreover, 1 exhibits strong luminescent emission in solid state at room temperature. Fluorescence quenching was observed when treating complex 1 with picric acid(PA), 2,4-dinitrophenylhydrazine(2,4-DNPH) and p-nitroaniline(p-NA), revealing that the as-synthesized complex could be used as a luminescence sensor for the detection of PA, 2,4-DNPH and p-NA.
基金Supported by the National Natural Science Foundation of China(No.21763028)Scientific Research Program Project of Yan’an University(No.YDY2017-07)+2 种基金Key Project of Natural Science of Shaanxi Provincial Education Department(No.16JS121)the Natural Science Foundation of Yan’an(2018KN-22)Yan’an University Training Program for Innovation and Entrepreneurship(No.D2018017)
文摘A new zinc coordination polymer（CP） {[Zn1.5（ttb）0.5（phen）（H2O）]·2 H2O}n（1）,（H6ttb = 3,4,5-tricarboxyl-（3?,4?,5?-tricarboxylazophenyl）benzene, phen = 1,10-phenanthroline）, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray determination, IR and thermogravimetric analysis（TGA）. CP 1 crystallizes in the monoclinic system, space group C2/c with a = 12.402（3）, b = 15.231（3）, c = 22.233（4） ?, β = 94.388（3）°, Zn1.5C21H16N3O9, Mr = 552.42, V = 4187.3（15） ?3, Dc = 1.753 g/cm3, F（000） = 2240, μ = 1.795 mm-1, S = 1.041, GOF = 1.041, Rint = 0.0169, 2.36°<θ<30.95°, and Z = 8. The final refinement gave R = 0.0340 and w R = 0.0927 for 5791 observed reflections with I > 2σ（I）. The completely deprotonated（ttb）6- ion in 1 adopts an octadentate coordination mode（μ8-η2-η1-η1-η1-η1-η2）. Four of the carboxyl groups are coordinated with four zinc ions by monodentate, respectively. While the other two carboxyl groups are coordinated with four zinc ions by bidentate, respectively. So, CP 1 possesses a 3 D network structure cross-linked by（ttb）6-ion. The XRD, UV and photoluminescence properties of CP 1 were also studied. Remarkably, 1 exhibits photocatalytic activities for the degradation of dye（MO） under UV light irradiation and shows good stabilities towards UV-light photocatalysis.
基金Supported by the National Natural Science Foundation of China(21763028)the Natural Science Foundation of Shaanxi Province(2018JM2055)
文摘Two metal-organic frameworks(MOFs) of formulae [Co7(L)3(4,4′-BPy)2(OH)2(H2O)6]·-4 H2O(1) and [Cd2(L)(2,2′-BPy)2]n(2, H4L = 5-(3,5-dicarboxybenzyloxy)-isophthalic acid,2,2′-BPy = 2,2?-bipyridine, 4,4′-BPy = 4,4′-bipyridine) were synthesized under solvothermal conditions. The structures of 1 and 2 were characterized by X-ray single-crystal diffraction analysis.In complex 1, six cobalt atoms were connected by oxygen atoms to form a defect dicubane structure. The defect dicubane structures were further linked by Co(4,4?-BPy) units to generate a3-D network structure. Compound 2 displays a 2-D chain structure. The photoluminescent property of complex 2 is investigated. The results show the exclusive luminescence emission bands being originated from intraligand π-π^* transitions.
基金the National Natural Science Foundation of China(No.21373178)。
文摘Two new complexes[Co_(2)(L)(4,4´-bip)(H_(2)O)_(3)]_(n)(1)and{[Co(L´)_(2)(phen)]·2H_(2)O)}_(n)(2)(H_(4)L=1-(3,5-dicarboxybenzyl)-3,5-pyrazole dicarboxylic acid,H_(3)L´=1-(3,5-dicarboxybenzyl)-3-pyrazole carboxylic acid,4,4´-bip=4,4´-bis(1-imidazolyl)biphenyl,phen=1,10-phenanthroline)were synthesized.Complexes 1 and 2 have been characterized by IR spectrography,X-ray single-crystal diffraction,elemental analysis and thermogravimetry.1 crystallizes in monoclinic system,space group P2_(1/c).Complex 2 crystallizes in monoclinic system,space group I2/a.It is remarkable that in situ hydrothermal decarboxylation was observed during preparing complex 2.In addition,magnetic analysis indicates that antiferromagnetic interaction exists among Co(Ⅱ)ions in complexes 1 and 2.
