Two new copper coordination polymers [Cu(μ2-4,4?-bipyridine)(NO2)2]n (C10H8- N4O4Cu, Mr = 311.75) 1 and [Cu(μ2-4,4?-bipyridine)2(H2O)2]n?2n(4,4?-bipyridine)?2nClO4?nH2O (C40H38N8O11Cl2Cu, Mr = 941.22) 2 were synthes...Two new copper coordination polymers [Cu(μ2-4,4?-bipyridine)(NO2)2]n (C10H8- N4O4Cu, Mr = 311.75) 1 and [Cu(μ2-4,4?-bipyridine)2(H2O)2]n?2n(4,4?-bipyridine)?2nClO4?nH2O (C40H38N8O11Cl2Cu, Mr = 941.22) 2 were synthesized by hydrothermal reaction and determined by X-ray diffraction method. Compound 1 crystallizes in monoclinic, space group P2/m with a = 4.7740(10), b = 11.039(2), c = 5.6752(14) ?, β = 91.394(9)o, V = 299.00(11) ?3, Z = 1, Dc = 1.731 g/cm3, F(000) = 157 and μ(MoKa) = 0.7107 mm-1. Compound 2 crystallizes in monoclinic, space group P2/n with a = 12.916(2), b = 11.149(1), c = 15.006(2) ?, β =106.642(6)o, V = 2070.3(5) ?3, Z = 2, Dc = 1.510 g/cm3, F(000) = 970 and μ(MoKa) = 0.7107 mm-1. In the structure of compound 1, the metal atom is in a slightly distorted octahedral CuO4N2 geometry surrounded by four O atoms of two NO2 ligands in the equatorial positions and two N atoms from 4,4?-bipyridine ligands in the axial sites, and the 4,4?-bipyridine ligands bridge the neighboring Cu2+ atoms to form polymeric chains in the lattice. Compound 2 has a 2D square-grid network structure. The square grids are superposed on each other to form a channel framework. The square cavity has dimensions of 11.148(2)? ×11.229(3)?. Every two guest 4,4?-bipyridine molecules are clathra- ted in each hydrophobic host cavity and further stabilized by π-π stacking and hydrogen bonding interactions.展开更多
Non-dispersive infrared （NDIR） and cavity ring-down spectroscopy （CRDS） CO2 analyzers use 12CO2 isotopologue absorption lines and are insensitive to all or part of other CO2-related isotopologues. This may produce...Non-dispersive infrared （NDIR） and cavity ring-down spectroscopy （CRDS） CO2 analyzers use 12CO2 isotopologue absorption lines and are insensitive to all or part of other CO2-related isotopologues. This may produce biases in CO2 mole fraction measurements of a sample if its carbon isotopic composition deviates from that of the standard gases being used. To evaluate and compare the effects of carbon isotopic composition on NDIR and CRDS CO2 analyzers, we prepared three test sample air cylinders with varying carbon isotopic abundances and calibrated them against five standard cylinders with ambient carbon isotopic composition using CRDS and NDIR systems. We found that the CO2 mole fractions of the sample cylinders measured by G1301 （CRDS） were in good agreement with those measured by LoFlo （NDIR）. The CO2 values measured by both instruments were higher than that of a CO2 isotope measured by G2201i （CRDS） analyzer for a test cylinder with depleted carbon isotopic composition δ^13C =-36.828%0, whereas no obvious difference was found for other two test cylinders with 3 δ^13C=-8.630‰ and δ^13C=-15.380‰, respectively. According to the theoretical and experimental results, we concluded that the total CO2 mole fractions of samples with depleted isotopic compositions can be corrected on the basis of their 12CO2 values calibrated by standard gases using LoFlo and G1301 if the fi13C and fi180 values are known. Keywords NDIR and CRDS analyzers, Carbon isotopic effects, CO2 measurements展开更多
基金This work was supported by the National Natural Science Foundation of China (No. 20173063) the State Key Basic Research and Development Plan of China (001CB108906) and the NSF of Fujian Province (E0020001)
文摘Two new copper coordination polymers [Cu(μ2-4,4?-bipyridine)(NO2)2]n (C10H8- N4O4Cu, Mr = 311.75) 1 and [Cu(μ2-4,4?-bipyridine)2(H2O)2]n?2n(4,4?-bipyridine)?2nClO4?nH2O (C40H38N8O11Cl2Cu, Mr = 941.22) 2 were synthesized by hydrothermal reaction and determined by X-ray diffraction method. Compound 1 crystallizes in monoclinic, space group P2/m with a = 4.7740(10), b = 11.039(2), c = 5.6752(14) ?, β = 91.394(9)o, V = 299.00(11) ?3, Z = 1, Dc = 1.731 g/cm3, F(000) = 157 and μ(MoKa) = 0.7107 mm-1. Compound 2 crystallizes in monoclinic, space group P2/n with a = 12.916(2), b = 11.149(1), c = 15.006(2) ?, β =106.642(6)o, V = 2070.3(5) ?3, Z = 2, Dc = 1.510 g/cm3, F(000) = 970 and μ(MoKa) = 0.7107 mm-1. In the structure of compound 1, the metal atom is in a slightly distorted octahedral CuO4N2 geometry surrounded by four O atoms of two NO2 ligands in the equatorial positions and two N atoms from 4,4?-bipyridine ligands in the axial sites, and the 4,4?-bipyridine ligands bridge the neighboring Cu2+ atoms to form polymeric chains in the lattice. Compound 2 has a 2D square-grid network structure. The square grids are superposed on each other to form a channel framework. The square cavity has dimensions of 11.148(2)? ×11.229(3)?. Every two guest 4,4?-bipyridine molecules are clathra- ted in each hydrophobic host cavity and further stabilized by π-π stacking and hydrogen bonding interactions.
基金supported by the International Science&Technology Cooperation Program of China(Grant Nos.2015DFG21960&2011DFA21090)the National Natural Science Foundation of China(Grant Nos.40905066,41175116,41273097,41505108&41505123)+2 种基金the CMA Climate Change Program(Grant No.CCSF201331),the CMA Operational Fund(Grant No.CMAGJ2013M73)the Graduate Research and Innovation Projects of Universities in Jiangsu Province(Grant No.KYLX_0834)the CAMS Fundamental Research Funds(Grant Nos.2014Y005,2015Y002&2014Z004)
文摘Non-dispersive infrared （NDIR） and cavity ring-down spectroscopy （CRDS） CO2 analyzers use 12CO2 isotopologue absorption lines and are insensitive to all or part of other CO2-related isotopologues. This may produce biases in CO2 mole fraction measurements of a sample if its carbon isotopic composition deviates from that of the standard gases being used. To evaluate and compare the effects of carbon isotopic composition on NDIR and CRDS CO2 analyzers, we prepared three test sample air cylinders with varying carbon isotopic abundances and calibrated them against five standard cylinders with ambient carbon isotopic composition using CRDS and NDIR systems. We found that the CO2 mole fractions of the sample cylinders measured by G1301 （CRDS） were in good agreement with those measured by LoFlo （NDIR）. The CO2 values measured by both instruments were higher than that of a CO2 isotope measured by G2201i （CRDS） analyzer for a test cylinder with depleted carbon isotopic composition δ^13C =-36.828%0, whereas no obvious difference was found for other two test cylinders with 3 δ^13C=-8.630‰ and δ^13C=-15.380‰, respectively. According to the theoretical and experimental results, we concluded that the total CO2 mole fractions of samples with depleted isotopic compositions can be corrected on the basis of their 12CO2 values calibrated by standard gases using LoFlo and G1301 if the fi13C and fi180 values are known. Keywords NDIR and CRDS analyzers, Carbon isotopic effects, CO2 measurements
