The inter-diffusion of N,N-dimethylformamide solution of Zn(phen)2Cl2 and (NH4)2MS4 (M = W, Mo) in an H-shape tube produced crystals of Zn(phen)2WS4 1 and Zn(phen)2MoS4 2 (phen = 1,10-phenanthroline). The structures o...The inter-diffusion of N,N-dimethylformamide solution of Zn(phen)2Cl2 and (NH4)2MS4 (M = W, Mo) in an H-shape tube produced crystals of Zn(phen)2WS4 1 and Zn(phen)2MoS4 2 (phen = 1,10-phenanthroline). The structures of isomorphous complexes 1 and 2 have been determined by X-ray single-crystal structure analyses. Four nitrogen atoms from the phenanthroline ligands and two sulfur atoms from the MS42- anion forming a distorted octahedron coordinate each zinc atom. Through p-p interactions of adjacent aromatic rings of the phenanthroline ligands, a quasi one-dimensional zigzag-stacking column is formed in each complex. Complex 1 crystallizes in monoclinic space group C2/c, with a = 10.447(8), b = 22.016(9), c = 12.824(8) ? b = 103.56(6)? V = 2867.7(8) 3, Z = 4, C24H16N4S4WZn, Mr=737.90, Dc = 1.71 g/cm3, F(000) = 1424, m = 5.25 mm-1, the final R = 0.054 and Rw = 0.075 for 2315 observations with I > 3s (I). Complex 2 crystallizes in monoclinic space group C2/c, with a = 10.410(6), b = 22.095(7), c = 12.830(6) ? b = 103.19(8)? V = 2873.1(5) 3, Z = 4, C24H16MoN4S4Zn, Mr=649.99, Dc = 1.50 g/cm3, F(000) = 1296, m = 1.58 mm-1, the final R = 0.072 and Rw = 0.100 for 1631 observations with I > 3s(I).展开更多
There are potentially huge amounts of water stored in Earth's mantle, and the water solubilities in the silicate minerals range from tens to thousands of part per minion(ppm, part per million). Exploring water in ...There are potentially huge amounts of water stored in Earth's mantle, and the water solubilities in the silicate minerals range from tens to thousands of part per minion(ppm, part per million). Exploring water in the mantle has attracted much attention from the societies of mineralogy and geophysics in recent years. In the subducting slab, serpentine breaks down at high temperature, generating a series of dense hydrous magnesium silicate(DHMS) phases, such as phase A, chondrodite, clinohumite, etc. These phases may serve as carriers of water as hydroxyl into the upper mantle and the mantle transition zone(MTZ). On the other hand, wadsleyite and ringwoodite, polymorphs of olivine, are most the abundant minerals in the MTZ, and able to absorb significant amount of water(up to about 3 wt.% H_2O). Hence, the MTZ becomes a very important layer for water storage in the mantle, and hydration plays important roles in physics and chemistry of the MTZ. In this paper, we will discuss two aspects of hydrous silicate minerals:(1) crystal structures and(2) equations of state(Eo Ss).展开更多
Multifunctional molecules are capable of assembling via different supramolecular synthons, or hydrogen bond motifs, between the same or different functional groups, leading to the possibility of cocrystal. Utilization...Multifunctional molecules are capable of assembling via different supramolecular synthons, or hydrogen bond motifs, between the same or different functional groups, leading to the possibility of cocrystal. Utilization of the interplay of dimensionality (I-D, 2-D and 3-D), orientation of functional groups of the building blocks, influence of rigid/flexible linking groups, and weak interactions provides an interesting route for the creation of novel supramolecular architectures in the crystal lattice. N-unsubstituted 1H-benzotriazole and carboxylic acid, being self-complementary molecules, offer a broad scope of study of binary compounds based on the complementary combination of H-bonding/donating sites. We report here the construction of three extended molecular networks in cocrystals of the carboxylic acid group of the acid and the 1H-benzotriazole triazole moiety. We have been able to identify four major supramolecualr synthons that would be helpful in the prediction of structural motifs for these kinds of studies. Interestingly, these heterosynthons are strikingly similar, to those of the homosynthons of the individual functional groups. The nature of the aza groups helps to enhance the overall volume of the crystal lattice thus lead- ing to the formation of various supramolecular assemblies. Thermal stability of these compounds has been investigated by thermogravimetric analysis (TGA) of mass loss.展开更多
Three new isostructural binuclear transition metal complexes with azido ion and 1,2-bis(3-(pyridin-2-yl)-lH-pyrazol-1- yl)ethane (bppe), formulated as [M2(N3)2(bppe)2](C104)2 (M = Co, 1; Ni, 2; Cu, 3), w...Three new isostructural binuclear transition metal complexes with azido ion and 1,2-bis(3-(pyridin-2-yl)-lH-pyrazol-1- yl)ethane (bppe), formulated as [M2(N3)2(bppe)2](C104)2 (M = Co, 1; Ni, 2; Cu, 3), were successfully synthesized. They were structurally and magnetically characterized. In 1-3, the double azido ions link two adjacent octahedral metal centers together in the end-to-on mode (EO), with the M-NEo-M angles of 99.41°, 100.24° and 99.80°, respectively. The co-ligand bppe acts as terminal ligand to saturate the remaining coordination sites. The magnetic properties of 1-3 have been investigated in the tem- perature range of 2-300 K. Fitting of the magnetic susceptibility data revealed the occurrence of the strong ferromagnetic in- teractions [J = 26.32 cm-1 (1), J = 38.23 cm-1 (2) and J = 139.83 cm-1 (3)]. Density functional theory calculations have been performed on 1-3 to provide a magneto-structural correlation of the ferromagnetic behavior.展开更多
基金grants from the National Natural Science Foundation of China the Natural Science Foundation of Fujian Province and Chinese Academy of Sciences.
文摘The inter-diffusion of N,N-dimethylformamide solution of Zn(phen)2Cl2 and (NH4)2MS4 (M = W, Mo) in an H-shape tube produced crystals of Zn(phen)2WS4 1 and Zn(phen)2MoS4 2 (phen = 1,10-phenanthroline). The structures of isomorphous complexes 1 and 2 have been determined by X-ray single-crystal structure analyses. Four nitrogen atoms from the phenanthroline ligands and two sulfur atoms from the MS42- anion forming a distorted octahedron coordinate each zinc atom. Through p-p interactions of adjacent aromatic rings of the phenanthroline ligands, a quasi one-dimensional zigzag-stacking column is formed in each complex. Complex 1 crystallizes in monoclinic space group C2/c, with a = 10.447(8), b = 22.016(9), c = 12.824(8) ? b = 103.56(6)? V = 2867.7(8) 3, Z = 4, C24H16N4S4WZn, Mr=737.90, Dc = 1.71 g/cm3, F(000) = 1424, m = 5.25 mm-1, the final R = 0.054 and Rw = 0.075 for 2315 observations with I > 3s (I). Complex 2 crystallizes in monoclinic space group C2/c, with a = 10.410(6), b = 22.095(7), c = 12.830(6) ? b = 103.19(8)? V = 2873.1(5) 3, Z = 4, C24H16MoN4S4Zn, Mr=649.99, Dc = 1.50 g/cm3, F(000) = 1296, m = 1.58 mm-1, the final R = 0.072 and Rw = 0.100 for 1631 observations with I > 3s(I).
基金supported by the National Natural Science Foundation of China(Grant Nos.41590621&41473058)the Fundamental Research Funds for the Central University(Grant No.G1323531512)MOST Special Fund from the State Key Laboratory of Geological Processes and Mineral Resources(Grant No.MSFGPMR07),China University of Geosciences at Wuhan
文摘There are potentially huge amounts of water stored in Earth's mantle, and the water solubilities in the silicate minerals range from tens to thousands of part per minion(ppm, part per million). Exploring water in the mantle has attracted much attention from the societies of mineralogy and geophysics in recent years. In the subducting slab, serpentine breaks down at high temperature, generating a series of dense hydrous magnesium silicate(DHMS) phases, such as phase A, chondrodite, clinohumite, etc. These phases may serve as carriers of water as hydroxyl into the upper mantle and the mantle transition zone(MTZ). On the other hand, wadsleyite and ringwoodite, polymorphs of olivine, are most the abundant minerals in the MTZ, and able to absorb significant amount of water(up to about 3 wt.% H_2O). Hence, the MTZ becomes a very important layer for water storage in the mantle, and hydration plays important roles in physics and chemistry of the MTZ. In this paper, we will discuss two aspects of hydrous silicate minerals:(1) crystal structures and(2) equations of state(Eo Ss).
基金supported by the National Natural Science Foundation of China (20701023 and 20971076)the Natural Science Foundation of Shandong Province,China (BS2010CL013 and2009ZRB019KH)
文摘Multifunctional molecules are capable of assembling via different supramolecular synthons, or hydrogen bond motifs, between the same or different functional groups, leading to the possibility of cocrystal. Utilization of the interplay of dimensionality (I-D, 2-D and 3-D), orientation of functional groups of the building blocks, influence of rigid/flexible linking groups, and weak interactions provides an interesting route for the creation of novel supramolecular architectures in the crystal lattice. N-unsubstituted 1H-benzotriazole and carboxylic acid, being self-complementary molecules, offer a broad scope of study of binary compounds based on the complementary combination of H-bonding/donating sites. We report here the construction of three extended molecular networks in cocrystals of the carboxylic acid group of the acid and the 1H-benzotriazole triazole moiety. We have been able to identify four major supramolecualr synthons that would be helpful in the prediction of structural motifs for these kinds of studies. Interestingly, these heterosynthons are strikingly similar, to those of the homosynthons of the individual functional groups. The nature of the aza groups helps to enhance the overall volume of the crystal lattice thus lead- ing to the formation of various supramolecular assemblies. Thermal stability of these compounds has been investigated by thermogravimetric analysis (TGA) of mass loss.
基金supported by grants from the National Natural Science Foundation of China (90922032, 21171100, 21151001)Ministry of Education (IRT0927)
文摘Three new isostructural binuclear transition metal complexes with azido ion and 1,2-bis(3-(pyridin-2-yl)-lH-pyrazol-1- yl)ethane (bppe), formulated as [M2(N3)2(bppe)2](C104)2 (M = Co, 1; Ni, 2; Cu, 3), were successfully synthesized. They were structurally and magnetically characterized. In 1-3, the double azido ions link two adjacent octahedral metal centers together in the end-to-on mode (EO), with the M-NEo-M angles of 99.41°, 100.24° and 99.80°, respectively. The co-ligand bppe acts as terminal ligand to saturate the remaining coordination sites. The magnetic properties of 1-3 have been investigated in the tem- perature range of 2-300 K. Fitting of the magnetic susceptibility data revealed the occurrence of the strong ferromagnetic in- teractions [J = 26.32 cm-1 (1), J = 38.23 cm-1 (2) and J = 139.83 cm-1 (3)]. Density functional theory calculations have been performed on 1-3 to provide a magneto-structural correlation of the ferromagnetic behavior.