Synthesis, Characterization and Quantum Chemical Calculation of Cobalt Coordination Polymer with 4,4′-bipy Bridge

Abstract

Abstract: A novel structure cobalt coordination polymer of {[Co(4,4′-bipy)(H₂O)₄]·(p-CH₃C₆H₄SO₃)₂}_n was prepared by solvothermal method with sodium p-toluenesulfonate as the main ligand and 4,4′-bipy as the auxiliary ligand. The cobalt coordination polymer was characterized by infrared spectroscopy, X-ray single crystal diffraction, thermogravimetric analysis and X-ray powder diffraction. The results show that {[Co(4,4′-bipy)(H₂O)₄]·(p-CH₃C₆H₄SO₃)₂}_n belongs to monoclinic system, P2₁/c space group; cell parameters of a=11.319 1(14)Å, b=8.062 6(11)Å, c=14.936(2)Å, α=90°, β=92.423(4)°, γ=90°, V=1 361.9(3)Å³, Z=2. The central metal Co(Ⅱ) ion is a hexagonal octahedral structure with slightly distorted coordination. It forms a one-dimensional infinite chain through the bridging of N atoms in 4,4′-bipy. The interlayer is further expanded into a three-dimensional supramolecular structure through the hydrogen bonding between the coordination water molecule and p-methylbenzenesulfonic acid. The [Co(4,4′-bipy)₂(H₂O)₄]·(p-CH₃C₆H₄SO₃) structural unit in the cobalt coordination polymer was quantum chemically calculated by Gaussian 09 program, and the optimal configuration was obtained. The atomic charge distribution and the composition of the front occupied orbital well support the coordination environment of the crystal structure. Finally, the electrochemical impedance test shows that the resistance of the coordination polymer is small and the conductivity is good, which provides a certain theoretical basis for its electrochemical application.

Key words: cobalt coordination polymer, solvothermal method, crystal structure, 4,4′-bipy, quantum chemical calculation

CLC Number:

O614.4

SHI Yiwei, YANG Ruijie, ZHANG Yingchun, WANG Xin, WANG Min, SONG Zhiguo. Synthesis, Characterization and Quantum Chemical Calculation of Cobalt Coordination Polymer with 4,4′-bipy Bridge[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(9): 1583-1590.

References

[1] ZHAO J J, DANG Z Y, MUDDASSIR M, et al. A new Cd(II)-based coordination polymer for efficient photocatalytic removal of organic dyes[J]. Molecules, 2023, 28(19): 6848.
[2] NORO S I, OCHI R, INUBUSHI Y, et al. CH₄/CO₂ and CH₄/C₂H₆ gas separation using a flexible one-dimensional copper(II) porous coordination polymer[J]. Microporous and Mesoporous Materials, 2015, 216: 92-96.
[3] KAHN O, PEI Y, VERDAGUER M, et al. Magnetic ordering of manganese(II) copper(II) bimetallic chains; design of a molecular based ferromagnet[J]. Journal of the American Chemical Society, 1988, 110(3): 782-789.
[4] QIN J S, ZHANG S R, DU D Y, et al. A microporous anionic metal-organic framework for sensing luminescence of lanthanide(III) ions and selective absorption of dyes by ionic exchange[J]. Chemistry-A European Journal, 2014, 20(19): 5625-5630.
[5] SUN C, XI R N, FEI H H. Organolead halide-based coordination polymers: intrinsic stability and photophysical applications[J]. Accounts of Chemical Research, 2023, 56(4): 452-461.
[6] EVANS O R, LIN W B. Crystal engineering of nonlinear optical materials based on interpenetrated diamondoid coordination networks[J]. Chemistry of Materials, 2001, 13(8): 2705-2712.
[7] HASEGAWA S, HORIKE S, MATSUDA R, et al. Three-dimensional porous coordination polymer functionalized with amide groups based on tridentate ligand: selective sorption and catalysis[J]. Journal of the American Chemical Society, 2007, 129(9): 2607-2614.
[8] DENG H X, DOONAN C J, FURUKAWA H, et al. Multiple functional groups of varying ratios in metal-organic frameworks[J]. Science, 2010, 327(5967): 846-850.
[9] CÔTÉ A P, SHIMIZU G K H. The supramolecular chemistry of the sulfonate group in extended solids[J]. Coordination Chemistry Reviews, 2003, 245(1/2): 49-64.
[10] ATWOOD J L, BARBOUR L J, HARDIE M J, et al. Metal sulfonatocalix[4, 5]arene complexes: bi-layers, capsules, spheres, tubular arrays and beyond[J]. Coordination Chemistry Reviews, 2001, 222(1): 3-32.
[11] LU W G, SU C Y, LU T B, et al. Two stable 3D metal-organic frameworks constructed by nanoscale cages via sharing the single-layer walls[J]. Journal of the American Chemical Society, 2006, 128(1): 34-35.
[12] DAYAL S, BURDA C. Semiconductor quantum dots as two-photon sensitizers[J]. Journal of the American Chemical Society, 2008, 130(10): 2890-2891.
[13] EOM G H, PARK H M, HYUN M Y, et al. Anion effects on the crystal structures of Zn^II complexes containing 2, 2'-bipyridine: their photoluminescence and catalytic activities[J]. Polyhedron, 2011, 30(9): 1555-1564.
[14] KIM Y, PARK B K, EOM G H, et al. Anion effects on construction of Zn^II compounds with a chelating ligand bis(2-pyridylmethyl)amine and their catalytic activities[J]. Inorganica Chimica Acta, 2011, 366(1): 337-343.
[15] SONG J H, LI X. Synthesis, crystal structure and properties of chain-like znic 4, 4′-bipy complex[J]. Chinese Journal of Inorganic Chemistry, 2009, 25(9): 1695-1698 (in Chinese).
[16] SU Y J, FAN T T, ZHANG M N, et al. 4, 4'-bipyridine bridged chain Zn(Ⅱ) complex: synthesis, crystal structure and fluorescence sensitization for Tb(Ⅲ) ion[J]. Spectroscopy and Spectral Analysis, 2018, 38(7): 2170-2174 (in Chinese).
[17] LIU D M, SU Y J, LI S S, et al. Transition metal coordination polymers constructed by 4-(4-carboxyphenoxy) isophthalic acid: synthesis, crystal structure, fluorescence sensing and photocatalysis[J]. Chemical Journal of Chinese Universities, 2020, 41(2): 253-261 (in Chinese).
[18] CAO M L, HE Y Q, LIU W T, et al. Crystal structure, electrochemistry and spectral properties of two 2-substituted-4, 6-di(2-pyridyl)-1, 3, 5-triazine bridged dinuclear ruthenium complexes[J]. Chinese Journal of Inorganic Chemistry, 2020, 36(11): 2135-2144 (in Chinese).
[19] CAO M L, SHANG M J, LIU W T, et al. Synthesis, spectroscopic and electrochemical properties of ruthenium(Ⅱ) polypyridyl complexes with dimethyl-bibenzimidazolate ligands[J]. Chinese Journal of Inorganic Chemistry, 2020, 36(9): 1763-1773 (in Chinese).
[20] LAN C L, LUO Z R, LI Y C. Synthesis, crystal structure and fluorescence of a novel zinc(Ⅱ) complex with 4-methylbenzenesulfonic acid and 4, 4′-bipyridine[J]. Chemical World, 2017, 58(1): 27-33 (in Chinese).
[21] LU T, CHEN F W. Multiwfn: a multifunctional wavefunction analyzer[J]. Journal of Computational Chemistry, 2012, 33(5): 580-592.
[22] HUMPHREY W, DALKE A, SCHULTEN K. VMD: visual molecular dynamics[J]. Journal of Molecular Graphics, 1996, 14(1): 27-28.
[23] MU Y J, WANG B Q, GAO Y, et al. Structure, electrochemical and fluorescent properties of a tubular cobalt complex[J]. Journal of University of Science and Technology Liaoning, 2023, 46(4): 273-278 (in Chinese).
[24] LI J P, HUANG Y Q, DAI H P, et al. Synthesis of nanoneedle-like Li₂MnSiO₄ cathode material for lithium-ion batteries and study on its electrochemical properties[J]. Modern Chemical Industry, 2024, 44(1): 114-119 (in Chinese).