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2016 Volume 35 Issue 1
2016, 35(1): 7-15
doi: 10.14102/j.cnki.0254-5861.2011-0684
Abstract:
Since 2-aminonicotinic acid is a zwitterionic molecule, the salt or co-crystal strategy was used for the precipitation under identical conditions and obtained two novel salts: salt 1 with 2:1:2 stoichiometry of 2-aminonicotinic acid:perchloric acid: H2O and salt 2 with 2:1:3 stoichiometry of 2-aminonicotinic acid: sulfuric acid: H2O. Their crystal structures were characterized by single-crystal X-ray diffraction, differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA). The structure determination shows that two salts are both primarily stabilized by the strong N-H…O hydrogen bonding interaction between 2-aminonicotinic acid and its corresponding acids. Constituents of the salt-crystalline phase were also investigated in terms of Hirshfeld surfaces. In the crystal lattice, a three-dimensional hydrogen-bonded network is observed, including the formation of a two-dimensional molecular scaffolding motif. Hirshfeld surfaces and fingerprint plots of two salts show that the structures are stabilized by H…H, O-H…O and C-O…π intermolecular interactions.
Since 2-aminonicotinic acid is a zwitterionic molecule, the salt or co-crystal strategy was used for the precipitation under identical conditions and obtained two novel salts: salt 1 with 2:1:2 stoichiometry of 2-aminonicotinic acid:perchloric acid: H2O and salt 2 with 2:1:3 stoichiometry of 2-aminonicotinic acid: sulfuric acid: H2O. Their crystal structures were characterized by single-crystal X-ray diffraction, differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA). The structure determination shows that two salts are both primarily stabilized by the strong N-H…O hydrogen bonding interaction between 2-aminonicotinic acid and its corresponding acids. Constituents of the salt-crystalline phase were also investigated in terms of Hirshfeld surfaces. In the crystal lattice, a three-dimensional hydrogen-bonded network is observed, including the formation of a two-dimensional molecular scaffolding motif. Hirshfeld surfaces and fingerprint plots of two salts show that the structures are stabilized by H…H, O-H…O and C-O…π intermolecular interactions.
2016, 35(1): 16-24
doi: 10.14102/j.cnki.0254-5861.2011-0602
Abstract:
Based on the full optimized molecular geometric structure at 6-311++G** level, the density (ρ), detonation velocity (D), and detonation pressure (P) for a new furazan-based energetic macrocycle compound, hexakis[1,2,5]oxadi-azole[3,4-c:3',4'-e;3'',4''-g:3''',4'''-k:3'''',4''''-m:3''''', 4'''''-o][1,2,9,10]-tetraazacyclohexadecine, were investigated to verify its capacity as high energy density material (HEDM). The infrared spectrum was also predicted. The heat of formation (HOF) was calculated using designed isodesmic reaction. The calculation on the bond dissociation energies (BDEs) was done and the pyrolysis mechanism of the compound was studied. The result shows that the N3-O1 bond in the ring may be the weakest one and the ring cleavage is possible to happen in thermal decomposition. The condensed phase HOF and the crystal density were also calculated for the title compound. The detonation data show that it can be considered as a potential HEDM. These results would provide basic information for the molecular design of novel high energy materials.
Based on the full optimized molecular geometric structure at 6-311++G** level, the density (ρ), detonation velocity (D), and detonation pressure (P) for a new furazan-based energetic macrocycle compound, hexakis[1,2,5]oxadi-azole[3,4-c:3',4'-e;3'',4''-g:3''',4'''-k:3'''',4''''-m:3''''', 4'''''-o][1,2,9,10]-tetraazacyclohexadecine, were investigated to verify its capacity as high energy density material (HEDM). The infrared spectrum was also predicted. The heat of formation (HOF) was calculated using designed isodesmic reaction. The calculation on the bond dissociation energies (BDEs) was done and the pyrolysis mechanism of the compound was studied. The result shows that the N3-O1 bond in the ring may be the weakest one and the ring cleavage is possible to happen in thermal decomposition. The condensed phase HOF and the crystal density were also calculated for the title compound. The detonation data show that it can be considered as a potential HEDM. These results would provide basic information for the molecular design of novel high energy materials.
2016, 35(1): 25-33
doi: 10.14102/j.cnki.0254-5861.2011-0821
Abstract:
5-(4-Cyclopropyl-5-((3-fluorobenzyl)sulfonyl)-4H-1,2,4-triazol-3-yl)-4-methyl-1,2,3-thiadiazole was synthesized and recrystallized from EtOH. The compound was characterized by 1H NMR, MS, elemental analysis and X-ray diffraction. The structure-active relationship and the antifungal activity based on density functional theory calculation (DFT) and antifungal activities were investigated. The compound crystallizes in the monoclinic space group P121/n1 with a = 8.929(3), b = 12.715(4), c = 15.161(5) Å, β = 106.142(3)°, V = 1653.3(9) Å3, Z = 4 and R = 0.0393 for 3930 observed reflections with I > 2σ(I). Theoretical calculation of the title compound was carried out with B3LYP/6-31G(d,p). The full geometry optimization was carried out using the 6-31G(d,p) basis set.The frontier orbital energy and atomic net charges were discussed. The observed results of the compound have been compared with theoretical results and the experimental data show good agreement with the calculated values. The compound exhibits good antifungal activity.
5-(4-Cyclopropyl-5-((3-fluorobenzyl)sulfonyl)-4H-1,2,4-triazol-3-yl)-4-methyl-1,2,3-thiadiazole was synthesized and recrystallized from EtOH. The compound was characterized by 1H NMR, MS, elemental analysis and X-ray diffraction. The structure-active relationship and the antifungal activity based on density functional theory calculation (DFT) and antifungal activities were investigated. The compound crystallizes in the monoclinic space group P121/n1 with a = 8.929(3), b = 12.715(4), c = 15.161(5) Å, β = 106.142(3)°, V = 1653.3(9) Å3, Z = 4 and R = 0.0393 for 3930 observed reflections with I > 2σ(I). Theoretical calculation of the title compound was carried out with B3LYP/6-31G(d,p). The full geometry optimization was carried out using the 6-31G(d,p) basis set.The frontier orbital energy and atomic net charges were discussed. The observed results of the compound have been compared with theoretical results and the experimental data show good agreement with the calculated values. The compound exhibits good antifungal activity.
2016, 35(1): 34-38
doi: 10.14102/j.cnki.0254-5861.2011-0857
Abstract:
The title compound 6-chloro-1-((6-chloropyridin-3-yl)methyl)-3-phenyl-1H-ben- zofuro[3,2-c]pyrazole (5, C21H13Cl2N3O, Mr = 394.26) was synthesized and characterized by elemental analysis, 1H NMR,13C NMR and X-ray single-crystal diffraction. The structure reveals that the crystal belongs to the triclinic system, space group P1 with a = 7.8829(8), b = 10.3281(10), c = 11.7615(12) Å, α = 83.5552(2), β = 79.921(2), γ = 70.189(2)°, V = 885.54(15) Å3, Z = 2, Dc = 1.479 g/cm3, μ = 0.383 mm-1, F(000) = 404, R = 0.0538 and wR = 0.1335 for 2453 observed reflections with I > 2σ(I). The result reveals that the crystal structure of the title compound 5 is stabilized by three C-Cl…π interactions and π…π stacking interaction. In addition, the preliminary investigation showed that 5 exhibits remarkably good antitumor activity against the MCF-7 and A549 cell lines.
The title compound 6-chloro-1-((6-chloropyridin-3-yl)methyl)-3-phenyl-1H-ben- zofuro[3,2-c]pyrazole (5, C21H13Cl2N3O, Mr = 394.26) was synthesized and characterized by elemental analysis, 1H NMR,13C NMR and X-ray single-crystal diffraction. The structure reveals that the crystal belongs to the triclinic system, space group P1 with a = 7.8829(8), b = 10.3281(10), c = 11.7615(12) Å, α = 83.5552(2), β = 79.921(2), γ = 70.189(2)°, V = 885.54(15) Å3, Z = 2, Dc = 1.479 g/cm3, μ = 0.383 mm-1, F(000) = 404, R = 0.0538 and wR = 0.1335 for 2453 observed reflections with I > 2σ(I). The result reveals that the crystal structure of the title compound 5 is stabilized by three C-Cl…π interactions and π…π stacking interaction. In addition, the preliminary investigation showed that 5 exhibits remarkably good antitumor activity against the MCF-7 and A549 cell lines.
2016, 35(1): 39-45
doi: 10.14102/j.cnki.0254-5861.2011-0817
Abstract:
A new organic-inorganic hybrid phosphotungstate-based CuII-ErIII heterometallic derivative [Cu(dap)2(H2O)][Cu(dap)2]4.5[Er(α-PW11O39)2]·4H2O (1, dap = 1,2-diaminopropane) has been hydrothermally prepared and characterized by elemental analysis, IR spectra and X-ray single-crystal diffraction. 1 belongs to the triclinic space group P with a = 13.453(3), b = 20.137(4), c = 24.565(4) Å, α = 103.468(4), β = 103.829(4), γ = 98.296(4)°, V = 6148.0(19) Å3, Z = 2, μ = 22.212 mm-1, GOOF = 1.030, R = 0.0744 and wR = 0.1700. Structural analysis indicates that 1 exhibits a special two-dimensional double-layer structure constructed from 1:2-type [Er(α-PW11O39)2]11- moieties and [Cu(dap)2]2+ linkers. From the topological viewpoint, 1 displays a scare two-dimensional five-connected topology in which the [Er(α-PW11O39)2]11- moieties function as the five-connected nodes. Furthermore, its thermogravimetric behavior has been studied.
A new organic-inorganic hybrid phosphotungstate-based CuII-ErIII heterometallic derivative [Cu(dap)2(H2O)][Cu(dap)2]4.5[Er(α-PW11O39)2]·4H2O (1, dap = 1,2-diaminopropane) has been hydrothermally prepared and characterized by elemental analysis, IR spectra and X-ray single-crystal diffraction. 1 belongs to the triclinic space group P with a = 13.453(3), b = 20.137(4), c = 24.565(4) Å, α = 103.468(4), β = 103.829(4), γ = 98.296(4)°, V = 6148.0(19) Å3, Z = 2, μ = 22.212 mm-1, GOOF = 1.030, R = 0.0744 and wR = 0.1700. Structural analysis indicates that 1 exhibits a special two-dimensional double-layer structure constructed from 1:2-type [Er(α-PW11O39)2]11- moieties and [Cu(dap)2]2+ linkers. From the topological viewpoint, 1 displays a scare two-dimensional five-connected topology in which the [Er(α-PW11O39)2]11- moieties function as the five-connected nodes. Furthermore, its thermogravimetric behavior has been studied.
2016, 35(1): 46-54
doi: 10.14102/j.cnki.0254-5861.2011-0805
Abstract:
Two novel acid-base adducts, [H2L12+](Hpbda)2 (1, L1 = 1,4-di(1H-imidazol-4-yl) benzene, H2pbda = 1,4-benzenedicarboxylic acid) and [H2L22+](NO3)2 (2, L2 = 1,4-di(1-carboxy- methyl-imidazol-4-yl)benzene), have been prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis. Compound 1 crystallizes in monoclinic, space group P21/n with a = 5.3525(11), b = 9.1471(19), c = 19.314(4) Å, β = 92.342(3)°, V = 944.8(3) Å3, Z = 2, C16H16N6O10, Mr = 452.35, Dc = 1.590 g/cm3, μ = 0.135 mm-1, S = 1.058, F(000) = 468, the final R = 0.0661 and wR = 0.1887 for 2298 observed reflections (I > 2σ(I)). Compound 2 crystallizes in monoclinic, space group P21/c with a = 9.6923(10), b = 17.2950(17), c = 7.1880(7) Å, β = 94.801(2)°, V = 1200.7(2) Å3, Z = 2, C28H22N4O8, Mr = 542.50, Dc = 1.501 g/cm3, μ = 0.112 mm-1, S = 1.060, F(000) = 564, the final R = 0.0394 and wR = 0.1017 for 2768 observed reflections (I > 2σ(I)). In the title compounds, both of L1 and L2 ligands act as weak base to accept protons to exhibit diprotonated H2L12+ and H2L22+ form, which can effectively employ as hydrogen bonding donors to combine anion moieties to form binary adducts respectively. In the crystal packing diagram of two polymers, there exist extensive noncovalent interactions including charge-transfer interactions, C(N)-H…π and N-H…O, C-H…O, O-H…O hydrogen bonding interactions between co-crystal moieties which consolidate the structures of supramolecular polymers, thus generating three-dimensional (3D) frameworks.
Two novel acid-base adducts, [H2L12+](Hpbda)2 (1, L1 = 1,4-di(1H-imidazol-4-yl) benzene, H2pbda = 1,4-benzenedicarboxylic acid) and [H2L22+](NO3)2 (2, L2 = 1,4-di(1-carboxy- methyl-imidazol-4-yl)benzene), have been prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis. Compound 1 crystallizes in monoclinic, space group P21/n with a = 5.3525(11), b = 9.1471(19), c = 19.314(4) Å, β = 92.342(3)°, V = 944.8(3) Å3, Z = 2, C16H16N6O10, Mr = 452.35, Dc = 1.590 g/cm3, μ = 0.135 mm-1, S = 1.058, F(000) = 468, the final R = 0.0661 and wR = 0.1887 for 2298 observed reflections (I > 2σ(I)). Compound 2 crystallizes in monoclinic, space group P21/c with a = 9.6923(10), b = 17.2950(17), c = 7.1880(7) Å, β = 94.801(2)°, V = 1200.7(2) Å3, Z = 2, C28H22N4O8, Mr = 542.50, Dc = 1.501 g/cm3, μ = 0.112 mm-1, S = 1.060, F(000) = 564, the final R = 0.0394 and wR = 0.1017 for 2768 observed reflections (I > 2σ(I)). In the title compounds, both of L1 and L2 ligands act as weak base to accept protons to exhibit diprotonated H2L12+ and H2L22+ form, which can effectively employ as hydrogen bonding donors to combine anion moieties to form binary adducts respectively. In the crystal packing diagram of two polymers, there exist extensive noncovalent interactions including charge-transfer interactions, C(N)-H…π and N-H…O, C-H…O, O-H…O hydrogen bonding interactions between co-crystal moieties which consolidate the structures of supramolecular polymers, thus generating three-dimensional (3D) frameworks.
2016, 35(1): 55-60
doi: 10.14102/j.cnki.0254-5861.2011-0831
Abstract:
The title compound 1-benzyl-5-((4-methoxyphenyl)ethynyl)-4-phenyl-1H-1,2,3-triazole (C24H19N3O) was designed and synthesized using one-pot strategy and structural characterization was done by single-crystal X-ray diffraction, NMR, IR and MS. This compound was crystallized out from an ethanolic solution in triclinic system, space group P with a = 9.9038(9), b = 10.2928(9), c = 18.8715(19) Å, α = 103.541(6), β = 90.507(7), γ = 97.157(7)°, V = 1854.2(3) Å3, Z = 4, crystal size (mm) = 0.25 × 0.1 × 0.1 and Rint = 0.068. Its asymmetric unit contains two independent molecules. The crystal structure of the title compound is stabilized by intramolecular interactions of types C-H…N and C-H…O. Additionally, X-ray analysis reveals obvious C-H…π, π-π stacking interactions between two adjacent aromatic ring planes.
The title compound 1-benzyl-5-((4-methoxyphenyl)ethynyl)-4-phenyl-1H-1,2,3-triazole (C24H19N3O) was designed and synthesized using one-pot strategy and structural characterization was done by single-crystal X-ray diffraction, NMR, IR and MS. This compound was crystallized out from an ethanolic solution in triclinic system, space group P with a = 9.9038(9), b = 10.2928(9), c = 18.8715(19) Å, α = 103.541(6), β = 90.507(7), γ = 97.157(7)°, V = 1854.2(3) Å3, Z = 4, crystal size (mm) = 0.25 × 0.1 × 0.1 and Rint = 0.068. Its asymmetric unit contains two independent molecules. The crystal structure of the title compound is stabilized by intramolecular interactions of types C-H…N and C-H…O. Additionally, X-ray analysis reveals obvious C-H…π, π-π stacking interactions between two adjacent aromatic ring planes.
2016, 35(1): 61-68
doi: 10.14102/j.cnki.0254-5861.2011-0948
Abstract:
Solvothermal reaction of Pb(NO3)2·6H2O with rigid linear ligand terephthalic acid (H2pta) in N,N-dimethylformamide (DMF) produced a new three-dimensional (3D) lead(II) coordination polymer [Pb2(pta)1.5(μ4-OH)(DMF)]n 1, and its structure was characterized by single-crystal X-ray diffraction analyses. In polymer 1, the μ4-OH bridges the nearby lead(II) ions into an infinite one-dimensional (1D) chain, and then the organic ligand pta2- joins the neighbored chains into a 3D structure by two similar connection modes in different configurations. The solid-state photoluminescent studies revealed that 1 exhibits a strong greenish emission mainly originating from ligand-to-metal charge transfer between the delocalized π bonds of the aromatic carboxylate ligand pta2- and the p orbitals of the Pb2+ centers.
Solvothermal reaction of Pb(NO3)2·6H2O with rigid linear ligand terephthalic acid (H2pta) in N,N-dimethylformamide (DMF) produced a new three-dimensional (3D) lead(II) coordination polymer [Pb2(pta)1.5(μ4-OH)(DMF)]n 1, and its structure was characterized by single-crystal X-ray diffraction analyses. In polymer 1, the μ4-OH bridges the nearby lead(II) ions into an infinite one-dimensional (1D) chain, and then the organic ligand pta2- joins the neighbored chains into a 3D structure by two similar connection modes in different configurations. The solid-state photoluminescent studies revealed that 1 exhibits a strong greenish emission mainly originating from ligand-to-metal charge transfer between the delocalized π bonds of the aromatic carboxylate ligand pta2- and the p orbitals of the Pb2+ centers.
2016, 35(1): 69-76
doi: 10.14102/j.cnki.0254-5861.2011-0900
Abstract:
The interaction of metal ions (Hg2+, Pb2+, Co2+, Mn2+) with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis(2-pyridyl)dipyrazino[2,3-f:20,30-h]quinoxaline (HPDQ) was investi- gated, and four new complexes have been synthesized and characterized. Complex 1 exhibits a 0 dimensional dual-core structure, 2 is a one-dimensional chain structure based on a dual-core Pb unit, while 3 and 4 show a 0 dimensional single-core structural unit. Complex 1 is of monoclinic system, space group C2/c with a = 19.211(4), b = 23.896(5), c = 12.698(3) Å, β = 120.11(3)°, V = 5043.0(17) Å3, Z = 4, S = 1.053, F(000) = 2976, Ra = 0.0637 and wRb = 0.1068 (I > 2σ(I)). Complex 2 adopts triclinic system, space group P1 with a = 10.370(2), b = 12.195(2), c = 21.033(4) Å, α = 80.87(3), β = 81.22(3), γ = 82.38(3)°, V = 2579.3(8) Å3, Z = 2, S = 1.099, F(000) = 1328, Ra = 0.0609 and wRb = 0.1365 (I > 2σ(I)). Complex 3 is of monoclinic system, space group C2/c with a = 14.166(3), b = 16.621(3), c = 20.248(4) Å, β = 92.18(3)°, V = 4764.0(16) Å3, Z = 4, S = 1.005, F(000) = 2108, Ra = 0.0589 and wRb = 0.1332 (I > 2σ(I)). Complex 4 belongs to the monoclinic system, space group C2/c with a = 14.404(3), b = 16.626(3), c = 20.346(4) Å, β = 92.43(3)°, V = 4868.2(17) Å3, Z = 4, S = 1.068, F(000) = 2108, Ra = 0.0833 and wRb = 0.1591 (I > 2σ(I)). Furthermore, the behavior of HPDQ with Hg2+, Pb2+, Co2+ and Mn2+ in the solution was also investigated, and the result shows after the metal ions were added respectively, the emission of all solutions shows fluorescence quenching and has a red shift compared with that of the HPDQ ligand.
The interaction of metal ions (Hg2+, Pb2+, Co2+, Mn2+) with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis(2-pyridyl)dipyrazino[2,3-f:20,30-h]quinoxaline (HPDQ) was investi- gated, and four new complexes have been synthesized and characterized. Complex 1 exhibits a 0 dimensional dual-core structure, 2 is a one-dimensional chain structure based on a dual-core Pb unit, while 3 and 4 show a 0 dimensional single-core structural unit. Complex 1 is of monoclinic system, space group C2/c with a = 19.211(4), b = 23.896(5), c = 12.698(3) Å, β = 120.11(3)°, V = 5043.0(17) Å3, Z = 4, S = 1.053, F(000) = 2976, Ra = 0.0637 and wRb = 0.1068 (I > 2σ(I)). Complex 2 adopts triclinic system, space group P1 with a = 10.370(2), b = 12.195(2), c = 21.033(4) Å, α = 80.87(3), β = 81.22(3), γ = 82.38(3)°, V = 2579.3(8) Å3, Z = 2, S = 1.099, F(000) = 1328, Ra = 0.0609 and wRb = 0.1365 (I > 2σ(I)). Complex 3 is of monoclinic system, space group C2/c with a = 14.166(3), b = 16.621(3), c = 20.248(4) Å, β = 92.18(3)°, V = 4764.0(16) Å3, Z = 4, S = 1.005, F(000) = 2108, Ra = 0.0589 and wRb = 0.1332 (I > 2σ(I)). Complex 4 belongs to the monoclinic system, space group C2/c with a = 14.404(3), b = 16.626(3), c = 20.346(4) Å, β = 92.43(3)°, V = 4868.2(17) Å3, Z = 4, S = 1.068, F(000) = 2108, Ra = 0.0833 and wRb = 0.1591 (I > 2σ(I)). Furthermore, the behavior of HPDQ with Hg2+, Pb2+, Co2+ and Mn2+ in the solution was also investigated, and the result shows after the metal ions were added respectively, the emission of all solutions shows fluorescence quenching and has a red shift compared with that of the HPDQ ligand.
2016, 35(1): 77-84
doi: 10.14102/j.cnki.0254-5861.2011-0826
Abstract:
The ionothermal reaction of Zn(NO3)2·6H2O with 5-sulfoisophthalic acid mono- sodium salt (NaH2SIP) and 1,2,4-triazole in 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) ionic liquid has afforded the compound {(EMIM)[Zn(SIP)]}n (1). The Zn(II) ions are linked by the carboxylate groups of SIP3- ligands to give a two-dimensional layered structure featuring the centrosymmetric dinuclear Zn2(µ2-COO)2 units. The adjacent two-dimensional layers are further linked by the Zn-O bonds between the Zn(II) ions and the sulfonate O atoms to generate a three-dimensional anionic [Zn(SIP)]nn- framework featuring one-dimensional open channels propagating along the a axis. The imidazolium cations [EMIM]+ derived from ionic liquid act as extraframework charge-balancing species for the anionic [Zn(SIP)]nn- framework and occupy the void space of the one-dimensional open channels. The rich ionic environments of the ionic liquid may be particularly helpful in the formation of the ionic compound 1. The roles of the ionic liquid in ionothermal synthesis and crystallization of the compound are briefly discussed. Furthermore, compound 1 displays a photoluminescent emission at 490 nm upon excitation at 406 nm.
The ionothermal reaction of Zn(NO3)2·6H2O with 5-sulfoisophthalic acid mono- sodium salt (NaH2SIP) and 1,2,4-triazole in 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) ionic liquid has afforded the compound {(EMIM)[Zn(SIP)]}n (1). The Zn(II) ions are linked by the carboxylate groups of SIP3- ligands to give a two-dimensional layered structure featuring the centrosymmetric dinuclear Zn2(µ2-COO)2 units. The adjacent two-dimensional layers are further linked by the Zn-O bonds between the Zn(II) ions and the sulfonate O atoms to generate a three-dimensional anionic [Zn(SIP)]nn- framework featuring one-dimensional open channels propagating along the a axis. The imidazolium cations [EMIM]+ derived from ionic liquid act as extraframework charge-balancing species for the anionic [Zn(SIP)]nn- framework and occupy the void space of the one-dimensional open channels. The rich ionic environments of the ionic liquid may be particularly helpful in the formation of the ionic compound 1. The roles of the ionic liquid in ionothermal synthesis and crystallization of the compound are briefly discussed. Furthermore, compound 1 displays a photoluminescent emission at 490 nm upon excitation at 406 nm.
2016, 35(1): 85-92
doi: 10.14102/j.cnki.0254-5861.2011-0800
Abstract:
Two new coordination polymers, [M6L3(DMA)3(H2O)] (M = Zn for 1, Cu for 2, L = tetrakis[3-(carboxyphenyl)oxamethyl]methane acid, DMA = N,N-dimethylacetamide) have been solvothermally synthesized. Single-crystal X-ray diffraction analysis reveals that compounds 1 and 2 are isostructural and crystallize in the trigonal space group R3. The asymmetrical unit contains two metal ions, one L4- ligand and two coordinated DMA molecules. The metal ions are connected through six aromatic rings into a linear trimetallic zinc building unit. The whole structure is connected through tetrehedral ligand and the trimetallic building units to form a 4,6-connected framework of the toc topology. Compounds 1 and 2 are further studied by IR spectroscopy, thermogravimetric analyses and PXRD. The solid-state UV-Vis and photoluminescent properties of compounds 1 are also investigated.
Two new coordination polymers, [M6L3(DMA)3(H2O)] (M = Zn for 1, Cu for 2, L = tetrakis[3-(carboxyphenyl)oxamethyl]methane acid, DMA = N,N-dimethylacetamide) have been solvothermally synthesized. Single-crystal X-ray diffraction analysis reveals that compounds 1 and 2 are isostructural and crystallize in the trigonal space group R3. The asymmetrical unit contains two metal ions, one L4- ligand and two coordinated DMA molecules. The metal ions are connected through six aromatic rings into a linear trimetallic zinc building unit. The whole structure is connected through tetrehedral ligand and the trimetallic building units to form a 4,6-connected framework of the toc topology. Compounds 1 and 2 are further studied by IR spectroscopy, thermogravimetric analyses and PXRD. The solid-state UV-Vis and photoluminescent properties of compounds 1 are also investigated.
2016, 35(1): 93-99
doi: 10.14102/j.cnki.0254-5861.2011-0809
Abstract:
The polymeric Co(II) complex [Co(Hdhpc)(py)]n (1) (py = pyridine, H3dhpc = 2,6-dihydroxypyridine-4-carboxyl acid) was prepared and characterized. X-ray diffraction data revealed that the compound crystallizes in dimorphic 1α and 1β forms at room and low temperature, respectively. The former crystallizes in the orthorhombic crystal system, space group Pbcm with a = 7.209(1), b = 14.834(3), c = 15.376(3) Å, V = 1644.3(5) Å3, Z = 4, C16H13CoN3O4, Mr = 370.22, Dc = 1.496 g/cm3, F(000) = 756, μ = 1.068 mm-1, R = 0.0633 and wR = 0.1192. While 1β is attributed to the monoclinic space group C2/c with a = 32.102(4), b = 7.022, c = 14.945(2) Å, β = 109.052(5)°, V = 3184.4(6) Å3, Z = 8, Dc = 1.544 g/cm3, F(000) = 1512, μ = 1.103 mm-1, R = 0.0428 and wR = 0.0797. The conformation changes of pyridines between Co-citrazinate planes leading to a reversible single-crystal to single-crystal transformation. The variable temperature magnetic data indicate a weak ferrimagnetism.
The polymeric Co(II) complex [Co(Hdhpc)(py)]n (1) (py = pyridine, H3dhpc = 2,6-dihydroxypyridine-4-carboxyl acid) was prepared and characterized. X-ray diffraction data revealed that the compound crystallizes in dimorphic 1α and 1β forms at room and low temperature, respectively. The former crystallizes in the orthorhombic crystal system, space group Pbcm with a = 7.209(1), b = 14.834(3), c = 15.376(3) Å, V = 1644.3(5) Å3, Z = 4, C16H13CoN3O4, Mr = 370.22, Dc = 1.496 g/cm3, F(000) = 756, μ = 1.068 mm-1, R = 0.0633 and wR = 0.1192. While 1β is attributed to the monoclinic space group C2/c with a = 32.102(4), b = 7.022, c = 14.945(2) Å, β = 109.052(5)°, V = 3184.4(6) Å3, Z = 8, Dc = 1.544 g/cm3, F(000) = 1512, μ = 1.103 mm-1, R = 0.0428 and wR = 0.0797. The conformation changes of pyridines between Co-citrazinate planes leading to a reversible single-crystal to single-crystal transformation. The variable temperature magnetic data indicate a weak ferrimagnetism.
2016, 35(1): 100-106
doi: 10.14102/j.cnki.0254-5861.2011-0804
Abstract:
A novel thiocyanate-controlled copper(II)-L-arginine complex with the formula of Cu(Arg)(SCN)2 (1, Arg: L-arginine) has been obtained from aqueous solution and structurally characterized by single-crystal X-ray diffraction method. Crystal data: orthorhombic, space group P212121, a = 6.0156(5), b = 12.1905(11), c = 18.4203(16) Å, V = 1350.8(2) Å3, Z = 4, μ = 1.933 mm-1, F(000) = 724, S = 1.084, the final R = 0.0410, wR = 0.0754 for 1893 observed reflections with I > 2σ(I), and R = 0.0559, wR = 0.0820 for all reflections. In addition, elemental analysis, IR, TG-DTG and magnetism characterization are presented.
A novel thiocyanate-controlled copper(II)-L-arginine complex with the formula of Cu(Arg)(SCN)2 (1, Arg: L-arginine) has been obtained from aqueous solution and structurally characterized by single-crystal X-ray diffraction method. Crystal data: orthorhombic, space group P212121, a = 6.0156(5), b = 12.1905(11), c = 18.4203(16) Å, V = 1350.8(2) Å3, Z = 4, μ = 1.933 mm-1, F(000) = 724, S = 1.084, the final R = 0.0410, wR = 0.0754 for 1893 observed reflections with I > 2σ(I), and R = 0.0559, wR = 0.0820 for all reflections. In addition, elemental analysis, IR, TG-DTG and magnetism characterization are presented.
2016, 35(1): 107-113
doi: 10.14102/j.cnki.0254-5861.2011-0806
Abstract:
Two new coordination polymers, [ZnL1]n (1, H2L1 = 5-(4-pyridyl)-methoxyl iso- phthalic acid) and [Ni(L2)2(H2O)4]n (2, HL2 = 4-(pyridin-4-ylmethoxy)benzolic acid), have been synthesized and characterized by elemental analysis, PXRD, IR spectra, and single-crystal X-ray diffraction. Compound 1 has a three-dimensional framework constructed by 6-bridged L12- anions connecting the Zn2(O2C)4 paddlewheel-like units. Compound 2 contains a mononuclear molecular unit, and the central nickel atom adopts a slightly distorted octahedral geometry by two nitrogen atoms from different L2- ligands and four oxygen atoms from water molecules. These molecular units link each other via four types of O-H…O hydrogen bonds to form an extended three-dimen- sional (3D) supramolecular network. The thermal and photoluminescent properties of 1 and 2 have also been investigated.
Two new coordination polymers, [ZnL1]n (1, H2L1 = 5-(4-pyridyl)-methoxyl iso- phthalic acid) and [Ni(L2)2(H2O)4]n (2, HL2 = 4-(pyridin-4-ylmethoxy)benzolic acid), have been synthesized and characterized by elemental analysis, PXRD, IR spectra, and single-crystal X-ray diffraction. Compound 1 has a three-dimensional framework constructed by 6-bridged L12- anions connecting the Zn2(O2C)4 paddlewheel-like units. Compound 2 contains a mononuclear molecular unit, and the central nickel atom adopts a slightly distorted octahedral geometry by two nitrogen atoms from different L2- ligands and four oxygen atoms from water molecules. These molecular units link each other via four types of O-H…O hydrogen bonds to form an extended three-dimen- sional (3D) supramolecular network. The thermal and photoluminescent properties of 1 and 2 have also been investigated.
2016, 35(1): 114-118
doi: 10.14102/j.cnki.0254-5861.2011-0816
Abstract:
An ionic iridium(III) complex [Ir(F2dpyb)(bzdpp)2Cl][OTf] with 1,3-difluoro- 4,6-di(2-pyridinyl) benzene (F2dpybH) terdentate ligand and benzyldiphenylphosphine (bzdpp) ligand was synthesized and characterized. The structure of iridium complex was verified by single-crystal X-ray crystallography. It crystallizes in monoclinic, space group P21/n with a = 14.3654(7), b = 23.0026(10), c = 15.7964(7) Å,β = 97.6029(11), V = 5173.9(4) Å3, Z = 4, F(000) = 2552, Dc = 1.645 Mg/m3, Mr = 1281.49 and μ = 0.071 mm-1. The UV-vis absorption and phosphorescence of the complex were discussed. The complex was ‘aggregation induced emission (AIE)’ active. It exhibited no emission in CH2Cl2 solution but strong blue-green emission in solid state under ultraviolet light excitation. The complex emitted a strong phosphorescence centered at 493 nm when doped in PMMA. Its lifetime is 0.755 μs and quantum yield is approximately 0.134.
An ionic iridium(III) complex [Ir(F2dpyb)(bzdpp)2Cl][OTf] with 1,3-difluoro- 4,6-di(2-pyridinyl) benzene (F2dpybH) terdentate ligand and benzyldiphenylphosphine (bzdpp) ligand was synthesized and characterized. The structure of iridium complex was verified by single-crystal X-ray crystallography. It crystallizes in monoclinic, space group P21/n with a = 14.3654(7), b = 23.0026(10), c = 15.7964(7) Å,β = 97.6029(11), V = 5173.9(4) Å3, Z = 4, F(000) = 2552, Dc = 1.645 Mg/m3, Mr = 1281.49 and μ = 0.071 mm-1. The UV-vis absorption and phosphorescence of the complex were discussed. The complex was ‘aggregation induced emission (AIE)’ active. It exhibited no emission in CH2Cl2 solution but strong blue-green emission in solid state under ultraviolet light excitation. The complex emitted a strong phosphorescence centered at 493 nm when doped in PMMA. Its lifetime is 0.755 μs and quantum yield is approximately 0.134.
2016, 35(1): 119-128
doi: 10.14102/j.cnki.0254-5861.2011-0815
Abstract:
Two novel coordination compounds, 1 [Zn4(L1)4(NO3)2(H2O)2](NO3)2·2H2O and 2 [Mn2(L2)2(DMF)(H2O)3](ClO4)2·DMF (HL1 = N'-[(1E)-pyridine-2-ylmethylidene]pyrazine-2- carbohydrazide, H2L2 = 2-hydroxy-3-methoxybenzaldehyde(pyrazin-2-ylcarbonyl)hydrazone), based on the N-N bridged ligands were prepared and structurally characterized. Compound 1 represents the [2*2] molecular squares, in which both N atoms belonging to the N-N bridged ligands are connected to the Zn centers. The emission of compound 1 exhibits a blue shift, which can be assigned to strong electrostatic interaction between ZnII ions and the L1-1. Compound 2 represents a rare phenol-O bridged Mn2II complex. The magnetic investigation indicates weak antiferromagnetic interactions between the MnII centers.
Two novel coordination compounds, 1 [Zn4(L1)4(NO3)2(H2O)2](NO3)2·2H2O and 2 [Mn2(L2)2(DMF)(H2O)3](ClO4)2·DMF (HL1 = N'-[(1E)-pyridine-2-ylmethylidene]pyrazine-2- carbohydrazide, H2L2 = 2-hydroxy-3-methoxybenzaldehyde(pyrazin-2-ylcarbonyl)hydrazone), based on the N-N bridged ligands were prepared and structurally characterized. Compound 1 represents the [2*2] molecular squares, in which both N atoms belonging to the N-N bridged ligands are connected to the Zn centers. The emission of compound 1 exhibits a blue shift, which can be assigned to strong electrostatic interaction between ZnII ions and the L1-1. Compound 2 represents a rare phenol-O bridged Mn2II complex. The magnetic investigation indicates weak antiferromagnetic interactions between the MnII centers.
2016, 35(1): 129-134
doi: 10.14102/j.cnki.0254-5861.2011-0788
Abstract:
One new chiral metal-organic coordination polymer, [Cd2(dpb)(H2hfipbb)2]n, was obtained under hydrothermal conditions of 1,3-di(pyridineyl)benzene (dpb) and 4,4'-(hexa- fluoroisopropylidene)bis(benzoic acid) (H2hfipbb). The title compound reveals a three-dimen- sional (3D) framework with two types of helical chains [Cd(COO)]n, which are linked each other to further form a double helical chain [Cd2(COO)2]n by sharing the same Cd(II) ions. The dpb connects the double helical chains to generate a 3D framework. These unique structures were studied by single-crystal X-ray and other spectroscopy techniques. In addition, the luminescent, fluorescence lifetime and second harmonic generation efficiency properties in the solid state have been studied.
One new chiral metal-organic coordination polymer, [Cd2(dpb)(H2hfipbb)2]n, was obtained under hydrothermal conditions of 1,3-di(pyridineyl)benzene (dpb) and 4,4'-(hexa- fluoroisopropylidene)bis(benzoic acid) (H2hfipbb). The title compound reveals a three-dimen- sional (3D) framework with two types of helical chains [Cd(COO)]n, which are linked each other to further form a double helical chain [Cd2(COO)2]n by sharing the same Cd(II) ions. The dpb connects the double helical chains to generate a 3D framework. These unique structures were studied by single-crystal X-ray and other spectroscopy techniques. In addition, the luminescent, fluorescence lifetime and second harmonic generation efficiency properties in the solid state have been studied.
2016, 35(1): 135-142
doi: 10.14102/j.cnki.0254-5861.2011-0797
Abstract:
A new binuclear ZnII coordination complex, Zn2(bta)(phen)2(Cl)3 (1, Hbta = 2-(1H- benzotriazol-1-yl)acetic acid and phen = 1,10-phenanthroline), has been synthesized and characteri- zed by single-crystal X-ray diffraction, IR spectroscopy, elemental, and photoluminescent analysis. Complex 1 crystallizes in triclinic system, space group P with a = 9.3040(19), b = 10.694(2), c = 16.841(3) Å, α = 101.18(3), β = 105.77(3), γ = 91.72(3)°, V = 1575.8(5) Å3, C32H22Zn2Cl3N7O2, Mr = 773.66, Dc = 1.631 g/cm3, Z = 2, F(000) = 780, μ = 1.820 mm-1, the final R = 0.1238 and wR = 0.1131. X-ray diffraction analyses indicate that 1 displays two crystallographic independent ZnII metal centers with a distorted tetragonal pyramidal (ZnN4O) and a tetrahedral (ZnNCl3) geometries, respectively. The phen serves as a common N,N'-bidentate ligand, and the bta- as a unique N,O-bridged ligand in 1. In the crystal, 1 forms a stable 3D supramolecular architecture by trifurcated hydrogen bonding C-H…Cl interactions and C-H…π, π…π stacking. 1 showed photo-electric conversion properties.
A new binuclear ZnII coordination complex, Zn2(bta)(phen)2(Cl)3 (1, Hbta = 2-(1H- benzotriazol-1-yl)acetic acid and phen = 1,10-phenanthroline), has been synthesized and characteri- zed by single-crystal X-ray diffraction, IR spectroscopy, elemental, and photoluminescent analysis. Complex 1 crystallizes in triclinic system, space group P with a = 9.3040(19), b = 10.694(2), c = 16.841(3) Å, α = 101.18(3), β = 105.77(3), γ = 91.72(3)°, V = 1575.8(5) Å3, C32H22Zn2Cl3N7O2, Mr = 773.66, Dc = 1.631 g/cm3, Z = 2, F(000) = 780, μ = 1.820 mm-1, the final R = 0.1238 and wR = 0.1131. X-ray diffraction analyses indicate that 1 displays two crystallographic independent ZnII metal centers with a distorted tetragonal pyramidal (ZnN4O) and a tetrahedral (ZnNCl3) geometries, respectively. The phen serves as a common N,N'-bidentate ligand, and the bta- as a unique N,O-bridged ligand in 1. In the crystal, 1 forms a stable 3D supramolecular architecture by trifurcated hydrogen bonding C-H…Cl interactions and C-H…π, π…π stacking. 1 showed photo-electric conversion properties.
2016, 35(1): 143-149
doi: 10.14102/j.cnki.0254-5861.2011-0795
Abstract:
A new Cd(II) coordination polymer, {[Cd(pda)(bimb)]·(H2O)0.5}n (1, H2pda = 1,3- phenylenediacetic acid, bimb = 4,4-bis(1-imidazolyl)biphenyl), has been synthesized and charac- terized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD) analyses and single-crystal X-ray diffraction techniques. Complex 1 shows a 4-connected two-fold interpene- trated three-dimensional (3-D) cds topology. In additional, photoluminescent properties of 1 and its dehydrated product have also been studied.
A new Cd(II) coordination polymer, {[Cd(pda)(bimb)]·(H2O)0.5}n (1, H2pda = 1,3- phenylenediacetic acid, bimb = 4,4-bis(1-imidazolyl)biphenyl), has been synthesized and charac- terized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD) analyses and single-crystal X-ray diffraction techniques. Complex 1 shows a 4-connected two-fold interpene- trated three-dimensional (3-D) cds topology. In additional, photoluminescent properties of 1 and its dehydrated product have also been studied.
2016, 35(1): 150-156
doi: 10.14102/j.cnki.0254-5861.2011-0791
Abstract:
Reaction of the ligand dmpt (dmpt = 6,7-dimethylbenzo[f][1,10]phenanthroline) with CuCl2 afforded mixed valent Cu(I)/Cu(II) discrete tetranuclear complexes [Cu(II)Cl2(dmpt)Cu(I)Cl] (1), while the reaction of ligand dppz (dppz = dipyrido[3,2-a:20,30-c] phenazine) with divalent halogen copper salt CuX2 (X = Cl, Br) gave one-dimensional chain mixed valent Cu(I)/Cu(II) complexes [Cu(II)Cl2(dppz)Cu(I)Cl]n (2) and discrete mixed valent Cu(I)/Cu(II) complexes [Cu(II)Br2(dppz)(DMF)Cu(I)Br] (3). Complex 2 consists of a one-dimensional chain -dppzCu(II)-Clμ2-Cu(I)-Cl-dppzCu(II)-Clμ2-Cu(I)- with Cu(II) and Cu(I) atoms linked together by chloride anion. Complex 3 is a discrete complex, which is the same as complexes 1 and 2 involving two different copper valent Cu(I) and Cu(II). The Cu(I) ion presents a pseudo-trihedral geometry, while the Cu(II) ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover, halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.
Reaction of the ligand dmpt (dmpt = 6,7-dimethylbenzo[f][1,10]phenanthroline) with CuCl2 afforded mixed valent Cu(I)/Cu(II) discrete tetranuclear complexes [Cu(II)Cl2(dmpt)Cu(I)Cl] (1), while the reaction of ligand dppz (dppz = dipyrido[3,2-a:20,30-c] phenazine) with divalent halogen copper salt CuX2 (X = Cl, Br) gave one-dimensional chain mixed valent Cu(I)/Cu(II) complexes [Cu(II)Cl2(dppz)Cu(I)Cl]n (2) and discrete mixed valent Cu(I)/Cu(II) complexes [Cu(II)Br2(dppz)(DMF)Cu(I)Br] (3). Complex 2 consists of a one-dimensional chain -dppzCu(II)-Clμ2-Cu(I)-Cl-dppzCu(II)-Clμ2-Cu(I)- with Cu(II) and Cu(I) atoms linked together by chloride anion. Complex 3 is a discrete complex, which is the same as complexes 1 and 2 involving two different copper valent Cu(I) and Cu(II). The Cu(I) ion presents a pseudo-trihedral geometry, while the Cu(II) ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover, halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.
2016, 35(1): 157-165
doi: 10.14102/j.cnki.0254-5861.2011-0813
Abstract:
Waste aluminum slag and oyster shell were used as raw materials to synthesize calcium hexaluminate (CA6). The effects of different source materials of CaO and sintering temperature on the structures and properties of CA6 were investigated, respectively. The results show that compared to calcium oxide, oyster shell can lower the formation temperature of CA6, hence CA6 can be detected at 1300 ℃ by using oyster shell as the starting raw materials. Increasing the sintering temperature can promote the crystal growth. CA6 crystals show typical platelet shape, and its optimum sintering temperature falls in the 1450～1550 ℃ region. The bulk density is 1.54～1.83 g/cm3, the apparent porosity is 44.1～55.2% and the flexural strength is 10.8～25.3 MPa.
Waste aluminum slag and oyster shell were used as raw materials to synthesize calcium hexaluminate (CA6). The effects of different source materials of CaO and sintering temperature on the structures and properties of CA6 were investigated, respectively. The results show that compared to calcium oxide, oyster shell can lower the formation temperature of CA6, hence CA6 can be detected at 1300 ℃ by using oyster shell as the starting raw materials. Increasing the sintering temperature can promote the crystal growth. CA6 crystals show typical platelet shape, and its optimum sintering temperature falls in the 1450～1550 ℃ region. The bulk density is 1.54～1.83 g/cm3, the apparent porosity is 44.1～55.2% and the flexural strength is 10.8～25.3 MPa.
2016, 35(1): 166-168
doi: 10.14102/j.cnki.0254-5861.2011-1077
Abstract:
An ultra-light and high porosity nano microfibril aerogel was prepared from konjac glucomannan (KGM) by the electrospinning and freeze-drying. The structure of aerogel was analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD) while the density and compressive strength of the samples were studied separately. Results reveal that porous network structure of the KGM nano microfibril aerogel is constructed by intermolecular hydrogen bonds in random and interpenetrate way. The nano microfibril structure presents in the KGM aerogel, which is an important reason of its high density and compressive strength. There is a potential application for this unique nano microfibril aerogel in the absorption of biodegradation bacteria to solve problems in marine oil spill pollution.
An ultra-light and high porosity nano microfibril aerogel was prepared from konjac glucomannan (KGM) by the electrospinning and freeze-drying. The structure of aerogel was analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD) while the density and compressive strength of the samples were studied separately. Results reveal that porous network structure of the KGM nano microfibril aerogel is constructed by intermolecular hydrogen bonds in random and interpenetrate way. The nano microfibril structure presents in the KGM aerogel, which is an important reason of its high density and compressive strength. There is a potential application for this unique nano microfibril aerogel in the absorption of biodegradation bacteria to solve problems in marine oil spill pollution.
