Syntheses,crystal structures,and quantum chemistry calculation of two Ni(Ⅱ)coordination polymers

Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.

A Modified Phase-Field Model for Polymer Crystal Growth

The irrationality of existing phase field model is analyzed and a modified phase-field model is proposed for polymer crystal growth, in which the parameters are obtained from real materials and very simple to use, and most importantly, no paradoxical parameters appeared in the model. Moreover, it can simulate different microstructure patterns owing to the use of a new different free energy function for the simulation of morphologies of polymer. The new free energy function considers both the cases of T〈Tm and T≥Tm, which is more reasonable than that in published literatures that all ignored the T≥Tm case. In order to show the validity of the modified model, the finite difference method is used to solve the model and different crystallization morphologies during the solidification process of isotactic polystyrene are obtained under different conditions. Numerical results show that the growth rate of the initial secondary arms is obviously increased as the anisotropy strength increases. But the anisotropy strength seems to have no apparent effect on the global growth rate. The whole growth process of the dendrite depends mainly upon the latent heat and the latent heat has a direct effect on the tip radius and tip velocity of side branches.

Synthesis and Crystal Structure of a Two-dimensional Coordination Polymer Constructed by Thiophene-2,5-dicarboxylic Acid and 1,4-Bis(imidazol-1-yl)-butane

A metal-organic coordination polymer [Cd（tdc）（bimb）（μ2-H2O）]n （H2tdc = thiophe-ne-2,5-dicarboxylic acid, bimb = 1,4-bis（imidazol-l-yl）-butane） 1 has been hydrothermally synthe- sized and characterized by elemental analysis, IR, TG, luminescence spectrum and single-crystal X-ray diffraction. Colorless crystals crystallize in the triclinic system, space group P^-1 with a = 5.8945（3）, b = 10.3129（5）, c = 11.2226（5） A, a = 95.1430（10）,β = 97.9020（10）, γ = 90.5910（10）°, V = 672.84（6） A^3, C11H11CdN2O5S, Mr= 395.68, De = 1.953 g/cm^3, μ（MoKa） = 1.797 mm^-1, F（000） = 390, Z = 2, the final R = 0.0209 and wR = 0.0508 for 2514 observed reflections （I 〉 2σ（I））. The structure of 1 exhibits a two-dimensional layer-like structure.

A phase-field model for simulating various spherulite morphologies of semi-crystalline polymers

A modified phase-field model is proposed for simulating the isothermal crystallization of polymer melts. The model consists of a second-order phase-field equation and a heat conduction equation. It obtains its model parameters from the real material parameters and is easy to use with tolerable computational cost. Due to the use of a new free energy functional form, the model can reproduce various single crystal morphologies of polymer melts under quiescent conditions, including dendritic, lamellar branching, ring-banded, breakup of ring-banded, faceted hexagonal, and spherulitic structures. Simulation results of isotactic polystyrene crystals demonstrate that the present phase-field model has the ability to give qualitative predictions of polymer crystallization under isothermal and quiescent conditions.

Synthesis and Crystal Structure of a New Two-dimensional Manganese Coordination Polymer:[Mn(L)(1,4-bdc)]

A new coordination polymer, [Mn（L）（1,4-bdc）] （L = 11-fluoro-dipyrido[3,2- a：2＂,3 ＂- c]phenazine, 1,4-bdc - benzene-1,4-dicarboxylate）, has been synthesized through the hydrothermal method and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.7544（9）, b = 10.8254（10）, c = 11.5288（10） A, a = 114.1300（10）, β = 96.6110（10）, y = 105.0390（10）°, V= 1038.62（16）/k3, Z= 2, C26H13FMnN404, Mr = 519.34, Dc = 1.661 g/cm3, F（000） = 526, ,u（MoKa） = 0.691 mm^-, R = 0.0405 and wR = 0.0977. The 1,4-bdc dianions link the neighboring Mn（II） atoms to yield a two-dimensional layer structure. The L ligands are attached on both sides of the layer. The π-π interactions between the L ligands of neighboring layers result in a three-dimensional supramolecular architecture.

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc(II) Coordination Polymer Assembled by Phthalate and 4,4′-Bipyridine

A metal-organic coordination polymer {[Zn（Pht）（4,4＇-bipy）（H2O）2]·2H2O}n （Pht = phthalate, 4,4＇-bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in the monoclinic system, space group P2/n, a = 7.6346（14）, b = 11.316（2）, c = 10.8133（19） ,A, β = 92.A.A,A.（3）°, V = 933.3（3） A^3, C18H20N2O8Zn, Mr = 457.73, Dc = 1.629 g/cm^3, F（000） = 472, Z = 2,μ（MoKa） = 1.367 mm^-1, the final R = 0.0323 and wR = 0.0821 for 1859 observed reflections （Ⅰ〉 2σ（Ⅰ））. The structure of 1 exhibits a two-dimensional bilayer framework formed by hydrogen bonding interactions. Furthermore, 1 shows yellow photoluminescent property at room temperature.

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Cu(phen)(2,4,6-TMBA)_2(H_2O)]_n

A one-dimensional chain coordination polymer [Cu（phen）（2,4,6-TMBA）2（H2O）]n has been synthesized by reacting 2,4,6-trimethyl-benzoic acid, 1,10-phenanthroline and Cu（Ⅱ） perchlorate and its structure was characterized. Crystal data for this complex： tetragonal, space group I41, a = 2.0293（3）, b = 2.0293（3）, c = 1.3758（2） nm, α =β= γ = 90°, V= 5.6657（13） nm3, Dc= 1.379 g/cm3, Z = 8, μ（MoKa） = 0.815 mm-1, Mr = 588.14, F（000） = 2456, S = 1.047, R = 0.0459 and wR = 0.1053. The crystal structure shows that two neighboring Cu（Ⅱ） ions are linked together by one bridging-chelating 2,4,6-trimethyl-benzoic group, forming a one-dimensional chain structure. Each Cu（Ⅱ） ion is coordinated with two nitrogen atoms from one 1,10-phenanthroline molecule, three oxygen atoms from three 2,4,6-trimethyl-benzoic acid molecules and one oxygen atom from one water molecule, giving a six-coordinate distorted octahedral coordination geometry. The cyclic voltammetry behavior of the complex was also investigated.

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a New Isophthalate- bridged Zinc(II) Polymer with One-dimensional Chain Structure: [Zn(ipt)(im)_2]_(2n)·3nH_2O (ipt = Isophthalate, im = Imidazole)

A new metal-organic coordination polymer [Zn（ipt）（im）2]2n·3nH2O 1 has been obtained by using hydrothermal synthesis and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P2（1/n） with a = 10.653（3）, b = 17.891（6）, c = 10.743（4）A^°,β= 117.093（5）°, V= 1822.9（10） A^°3, Mr= 413.65, Dc = 1.507 g/cm^3,/t（MoKa） = 1.390 mm^-1, F（000） = 840, Z = 4, the final R = 0.0444 and wR = 0.1066 for 2434 observed reflections （I〉 2σ（I））. Furthermore, compound 1 shows blue photoluminescent property at room temperature.

Syntheses, Crystal Structures and Magnetic Properties of Ni(Ⅱ) and Mn(Ⅱ) Coordination Polymers Constructed from 5-(2'-Carboxylphenyl) Nicotate and 2,2'-Biimidazole

Two coordination polymers, namely {[Ni（cpna）（H2biim）（H2O）]·H2O}n （1） and {[Mn（cpna）（H2biim）]·H2O}n （2） （H2cpna = 5-（2＇-carboxylphenyl） nicotic acid, H2biim = 2,2＇- biimidazole）,have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. Compound 1 exhibits a one- dimensional （1D） step-like chain structure, which further builds a three-dimensional （3D） supramolecular architecture via O–HAAAO and N–HAAAO hydrogen-bonding and π-π stacking interactions. Compound 2 possesses a one-dimensional （1D） double chain structure, which is further assembled into a 3D supramolecular framework by N–HAAAO hydrogen bonding and π-π stacking interactions. Magnetic susceptibility measurement indicates that compound 1 shows a weak antiferromagnetic coupling between the nearest Ni（II） centers, with g = 2.11 and J = –1.87 cm^-1.

Synthesis, Crystal Structure and Luminescent Property of a Ag(Ⅰ) Coordination Polymer with a 3D Sandwich-like Framework

A new coordination polymer,{[Ag2（bpp）2（H2O）2]·bpdc·3H2O}n,derived from the ligand biphenyl-4,4＇-dicarboxylic acid（H2bpdc）,has been obtained through a hydrothermal technique（bpp = l,3-bis（4-pyridyl）propane）.Its single-crystal structure has been characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TGA and elemental analysis techniques.The single-crystal X-ray diffraction reveals that complex 1 consists of 1D infinite[Ag（bpp）（H2O）]n^（n＋）cationic chains,2D anionic layer constructed by bpdc anions and free water which provide charge compensation in the crystal structure.The 1D infinite[Ag（bpp）（H2O）]n^（n＋） cationic chains and 2D anionic layer are further stacked in-ABAB- fashion through intermolecular H-bonding to form a 3D sandwich-like framework.In addition,the luminescent property of complex 1 in the solid state at room temperature was investigated.

Hydrothermal Synthesis and Crystal Structure of a Cobalt(II) Coordination Polymer: [Co(C_2O_4)(bix)]_n (bix = 1,4-Bis(imidazol-1-ylmethyl)-benzene)

A new two-dimensional cobalt coordination polymer has been prepared and fully characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The compound [Co（C2O4）（bix）]n 1 crystallizes in the monoclinic system, space group C2/c, with a = 11.549（3）, b = 15.700（3）, c = 9.260（2） A, β = 102.984（3）°, V = 1636.0（6） A^3, C16HIaCON4O4, Mr= 383.23, Dc = 1.556 g/cm^3, μ（MoKa） = 1.078 mm^-1, F（000） = 780, Z = 4, the final R = 0.0455 and wR = 0.1286 for 1483 observed reflections （I 〉 2σ（I））. Of the compound, the Co center is octahedrally coordinated with oxalate acting as a tetra-dentate ligand coordinated to the cobalt atom and each bix serving as a bridging ligand by employing two N-donors to coordinate with the Co center. An infinite {Co2（C2O4）2}∞ chain is formed along the α axis. Furthermore, the 1D chains are held together via bix ligands to generate a two-dimensional network structure with 1D coronal-like channels （ca. 5.691A × 15.700A）.

Hydrothermal Synthesis and Crystal Structure of a New Three-dimensional Heterometallic Coordination Polymer

A new 3d-4fheterometallic polymer {[Sm2Cu（PDC）2（SO4）2（H20）6]·2H2O}n 1 has been synthesized by Sm2O3, Cu（SO4）2·5H2O and pyridine-3,5-dicarboxylic acid under hydrothermal conditions. The compound crystallizes in triclinic system, space group Pi, with a = 6.352（7）, b = 10.040（10）, c = 10.315（11） A, α = 94.958（14）, β = 95.556（7）, γ = 99.747（14）°, V = 641.7（12）A3, Z = 1, M, = 1030.63, Dc= 2.651 Mg/m3,μ = 5.615 mm-1, F（000） = 491, the final R = 0.0491 and wR = 0.1345 for 2098 observed reflections with I 〉 2σ（I）. The compound is a three-dimensional network structure in which infinite lanthanide-carboxylate chains are linked by [Cu（$04）2]2- metalloligands to form a mixed-metal coordination network.

Hydrothermal Synthesis and Crystal Structure of a Novel Isophthalate-bridged Copper(II) Polymer with Two-dimensional Network Structure: [Cu_2(phen)(ipt)_2]_(2n)·nH_2O (ipt = isophthalate, phen = 1,10-phenanthroline)

A novel metal-organic coordination polymer [Cu2（phen）（ipt）2]2n-nH2O 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 12.338（3）, b = 12.167（3）, c = 18.167（4）A, β= 111.686（14）°, V = 2534.1（10）A^3, C28H18Cu2N2O9, Mr = 653.52, Dc = 1.713 g/cm^3,μ（MoKα） = 1.740 mm^-1, F（000） = 1320, Z = 4, the final R = 0.0443 and wR = 0.0853 for 3543 observed reflections （1 〉 2σ（I））. It exhibits a novel two-dimensional network with tetra-Cu-ipt-as building units.

Urothermal Synthesis and Crystal Structure of a Zn(Ⅱ) Coordination Polymer with a 3-D Supramolecular Structure

A new metal-organic coordination polymer [Zn（hfipbb）（e-urea）]n（1,H2hfipbb = 4,4＇-（hexafluoroisopropylidene）bis（benzoic acid）,e-urea = ethylene urea） has been urothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction.The title complex crystallizes in monoclinic,space group P21/c with a = 13.302（4）,b = 10.981（3）,c = 13.804（4） ,β = 93.587（5）°,V = 2012.3（10） 3,C20H14N2O5F6Zn,Mr = 541.72,Z = 4,Dc = 0.447 g/cm3, = 0.328 mm-1,F（000） = 272,R = 0.0340 and wR = 0.1107 for 4528 observed reflections（I 〉2σ（I））.In the structure of compound 1,two Zn（Ⅱ） ions are bridged by two carboxylate groups from two hfipbb ligands to form a dinuclear unit,and each dinuclear Zn（Ⅱ） unit is linked with its two adjacent dinuclear units through four hfipbb ligands into an infinite one-dimensional double-chain.The interesting structural feature of compound 1 is that the one-D double-chains are self-interconnected into a three-D supramolecular structure through hydrogen bonds between the coordinated e-urea molecules and carboxylate oxygen atoms（N1 and O2,N2 and O4）.

Hydrothermal Synthesis and Crystal Structure of a Zinc(II) Polymer with a Two-dimensional Layer Structure: [Zn(pzdc)(phen)]_n·nH_2O

A metal-organic coordination compound formulated as [Zn（pzdc）（phen）]n·nH2O 1 （H2pzdc = pyrazine-2,3-dicarboxylic acid, phen = 1,10-phenanthroline） has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/n with a = 11.607（2）, b = 11.719（2）, c = 13.140（3）A^°, β = 110.707（3）°, V= 1671.9（6）A^°3, C18H12ZnN4O5, Mr= 429.69, De = 1.707 g/cm^3,μ（MoKa） = 1.511 mm^-1, F（000） = 872, Z = 4, the final R = 0.0356 and wR = 0.0853 for 2713 observed reflections （I 〉 2σ（I））. It exhibits an interesting two-dimensional layer structure and shows yellow photoluminescent property at room temperature.

Hydrothermal Synthesis and Crystal Structure of a Cadmium(II) Polymer with One-dimensional Chain Structure: [Cd(bpy)(BDC)]_n·nbpy

A metal-organic coordination polymer [Cd（bpy）（BDC）]n·nbpy （bpy = 2,2-bipyri-dine, H2BDC = terephthalic acid） has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group C2/c with a = 15.723（5）, b = 21.695（5）, c = 7.576（5） A, β = 116.171（7）°, V = 2319.3（18）A^3, C28H20CdN4O4, Mr = 588.88, Dc = 1.686 g/cm^3, μ（MoKα） = 0.987 mm^-1, F（000） = 1184, Z = 4, the final R = 0.0464 and wR = 0.0831 for 1882 observed reflections （Ⅰ〉 2σ（Ⅰ））. It exhibits a three-dimensional network with channels constructed from one-dimensional coordination chains via C–H…O hydrogen bonds and significant aromatic π-π stacking interactions.

Synthesis and Crystal Structure of a 1D Chained Coordination Polymer Containing One-dimensional Egg-like Channels:{[Cu_2(C_2O_4)_2(inta)_4](inta)}_n (inta=Isonicotinamide)

A new one-dimensional copper coordination polymer chain has been prepared and fully characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The compound { [Cu2（C2O4）2（inta）4]（inta）}n 1 crystallizes in the triclinic system, space group P1, with a = 8.4722（5）, b = 10.9825（6）, c = 11.6128（6）A, α= 104.8050（10）,β = 102.5740（10）, γ= 109.6890（10）°, V= 927.18（9） A3, Mr = 929.79, Z = 1, Dc = 1.665 g/cm^3, F（000） = 475, μ = 1.231 mm^-1, R = 0.0453 and wR = 0.1185 for 3290 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Of the compound, the Cu center is octahedrally coordinated with oxalate acting as a tetra-dentate ligand coordinated to the copper atom and each inta serving as a terminal ligand by employing only one N-donor to coordinate with the Cu center. An infinite {Cu2（C2O4）2}∞ chain is formed along the c axis. Furthermore, the 1D chains are held together via extensive hydrogen-bonding interactions to generate a three-dimensional network with 1D channels （ca. 5.491A×11.507A） where inta molecules are filled.

Synthesis, Crystal Structure and Fluorescent Properties of a New One-Dimensional Polymer [Sm(sal)_4(phen)_2Na]_n

The title complex, [Sm(sal)_4(phen)_2Na]_n (Ⅰ), where Hsal=salicylic acid, phen=1, 10-phenanthroline, was synthesized by the reaction of samarium chloride with phen and Hsal in ethanol solution and its crystal structure was determined by X-ray diffraction. The crystal is monoclinic, space group C2/c with cell dimensions of a=2 84989 (7) nm, b=0 93347 (2) nm, c=2.27954 (5) nm, β=132.4010 (8)°, V=4.4781 (2) nm^3, Z=4, μ (Mo Kα)=13.97 cm^(-1), D_c=1.605 g·cm^(-3). The title complex is a compound, with centre of the Sm and Na atoms which are bridged by two carboxylate ligands. The structure of the complex demonstrates one-dimensional chain bridged by carboxyl groups. The fluorescence spectrum of the complex indicates that the second ligand phen shows enhancement effect on the fluorescence of the complex.

Synthesis and Crystal Structure of a Novel 2-Fold Interpenetrating Three-dimensional Coordination Polymer,{[Co_3(byip)_2(bix)_3(H_2O)_2]·H_2O}_n

The title coordination polymer including two crystallographically independent Co2＋ ions is hydrothermally synthesized, in which the Co（1） 2＋ ion is four-coordinated by two carboxylate oxygen atoms from two different 5-（benzoic acid-4-yldiazenyl）isophthalate （byip3-） anions and two nitrogen atoms from two distinct 1,4-bis（imidazol-1-ylmethyl） benzene （bix） ligands displaying a tetrahedral geometry. The Co（2） 2＋ ion is six-coordinated by two water molecules at the apical positions, and two carboxylate oxygen atoms and two nitrogen atoms at the equatorial positions, affording a slightly distorted octahedron. Two Co（1）2＋ and two Co（2）2＋ ions are linked together by four byip3- anions forming a 44-membered motif and these motifs are further arranged into a three-dimensional framework through bix ligands along the a axis with a larger channel （ca. 22.70×11.01）. Each individual network interpenetrates with the other identical network in a parallel fashion to generate a 2-fold interpenetrating array with the {62.84}{63}2{64.82}2 topology.

Hydrothermal Synthesis and Crystal Structure of a 1D Cu(II) Coordination Polymer: [Cu(bbpy)(H_2bptc)]_n Constructed by a Tetracarboxylic Acid

The title compound [Cu（bbpy）（H2bptc）]n （bbpy = 4,4＇-dimethyl-2,2＇-bipyridine and H4bptc = 1,1＇-biphenyl-2,2？,3,3＇-tetracarboxylic acid） has been synthesized by hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of triclinic, space group P1 with a = 11.2831（12）, b = 11.6718（13）, c = 11.7771（13）, α = 105.392（2）, β = 108.382（2）, γ = 112.397（2）o, CuC28H20N2O8, Mr = 576.00, V = 1222.4（2）3, Dc = 1.565 g/cm3, F（000） = 590, μ = 0.951 mm-1, S = 1.022 and Z = 2. The final refinement gave R = 0.0405 and wR = 0.1142 for 4270 observed reflections with I 2σ（I）. The title complex has a 1D [Cu（bbpy）（H2bptc）]n chain structure, in which the extensive hydrogen-bond interactions make the chain more stable. The neighboring parallel chains are further packed into a 2D layer structure via π···π stacking interaction between the pyridine rings of bbpy ligands. Moreover, the adjacent layers are interconnected by the C–H···π interactions to form a 3D metal-organic framework.