Synthesis,crystal structure and third-order non-linear optical properties of a Zn(II) two-dimensional polymer

Two-dimensional (2-D) metal-organic polymer [Zn₃(μ₂-4,4′-bipy)₂(μ₂-be)₂(be)₂(μ₂-N₃)₂]_n 1 (4,4′-bipy = 4,4′-bipyridine, be = benzoate, N₃^? = azide anion) has been synthesized by low-hot reaction and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and UV–visible spectra. The 2-D structure is built from the linkage of secondary building units of trinuclear [Zn₃(μ₂-4,4′-bipy)₂(μ₂-be)₂(be)₂(μ₂-N₃)₂] clusters by a mixed connector of 4,4′-bipyridine, benzoate and azide. The third-order non-linear optical (NLO) properties of the 1 were also investigated with modulus of the hyperpolarizability (γ) 8.51 × 10^?30 esu for 1 in a 3.17 × 10^?4 mol dm^?3 DMF solution.     

Heterometallic copper(Ⅱ) vanadates: synthesis,crystal structures and third-order nonlinear optical properties

Three polymeric heterometallic clusters with 1D, 2D, and 3D frameworks, constructed from a cyclic vanadate {V4O12}4-building block and three geometric constraint ligands, were synthesized by a one-pot self-assembly reaction. Z-scan experiments demonstrated that all the three cluster polymers have large hyperpolarizability γ values. TD-DFT calculations afforded insight into the electronic transitions and spectral characterization of these novel NLO molecular materials.     

Synthesis,crystal structure,and catalytic properties of a one-dimensional nickel(II) polymer

The title complex [Ni₂(C₁₀H₉N₃)₂(C₁₄H₈O₅)₂] _n , which has an inversion center, midway between two Ni(II) atoms forms a one-dimensional polymer bridged by 4,4′-oxydibenzoate ligands with a Ni…Ni separation of 14.4705(11) Å. The Ni(II) atom is six-coordinated by two N atoms of a bis(2-pyridyl)amine ligand and four O atoms from two 4,4′-oxydibenzoate ligands, to form a distorted octahedron coordination geometry and then are linked via N-H…O and C-H…O hydrogen bonding into a polymeric ribbon structure. The activity and selectivity profiles of the polymer indicate that the optimization temperature and time span are 175°C and 30–40 min for the dehydration of cyclohexanol, respectively.     

Synthesis,crystal structure,and luminescence properties of a one-dimensional europium(III) polymer

In the title complex, [Eu₂(C₈H₇O₃)₆(C₁₂H₈N₂)₂] _n , which has an inversion center midway between two Eu(III) atoms of the structural unit, forms a one-dimensional polymer bridged by two mondentate, two bidentate, and two tridentate carboxylate groups with an Eu-Eu separation of 4.1853(7) Å. Each Eu atom is nine-coordinated by two N atoms of a 1,10-phenanthroline (phen) ligand and seven O atoms from six phenoxyacetate ligands, to form a distorted tricapped trigonal prismatic. The luminescence spectrum of the polymer indicates that the intensity of the emission wavelength at 619 nm is the strongest among all emission wavelengths and the second phen ligand shows an enhancement effect on the luminescence of the complex.     

Synthesis,crystal structure and properties of a one-dimensional polymeric copper(II) complex of tetrachlorophthalate

The coordination polymer [Cu₂L₂(H₂O)₆ · 2(H₂O)] _n (L = -tetrachlorophthalate dianion) has been synthesized and characterized by X-ray crystallography, i.r. spectroscopy, electronic spectroscopy and cyclic voltammetry. The structure of the complex is a one-dimensional zigzag chain. The i.r. spectra reveal that the tetrachlorophthalate groups are bismonodentate ligands, and this is confirmed by the crystal structure determination. Cyclic voltammetry reveals two steps of a quasi-reversible oxidation–reduction processes for the complex.     

Synthesis,crystal structure,and third-order non-linear optical properties of a new Cd(II) polymer constructed from pyrazine-2-carboxylic acid

A new cadmium(II) pyrazine-2-carboxylate coordination polymer, {[Cd(L)(H₂O)₂(SO₄)_0.5]₂·H₂O}_n (1) (HL = pyrazine-2-carboxylic acid), has been synthesized by low-temperature solid-state reaction. Single-crystal X-ray analyses reveal that 1 possesses a 3-D framework structure. The polymer 1 was characterized by elemental analyses, thermogravimetric analyses, X-ray powder diffraction analyses, IR spectra, and UV–visible spectra. The third-order non-linear optical properties were also investigated and they exhibit nice non-linear absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 1.30 × 10^?30 esu for 1 in a 2.01 × 10^?4 M?dm^?3 DMF solution.     

Synthesis,crystal structures,and third-order nonlinear optical properties of a series of ferrocenyl organometallics

Three novel ferrocenyl complexes [Zn(4-PFA)(2)(NO(3))(2)](H(2)O) (1), [Hg(2)(OAc)(4)(4-BPFA)(2)](CH(3)OH) (2), and [Cd(2)(OAc)(4)(4-BPFA)(2)] (3) (4-PFA = [(4-pyridylamino)carbonyl]ferrocene, 4-BPFA = 1,1'-bis[(4-pyridylamino)carbonyl]ferrocene) were prepared, and complexes 1 and 2 were structurally characterized by means of X-ray single-crystal diffraction. In complex 1, the zinc(II) atom is coordinated at a distorted tetrahedral environment by two nitrogen atoms from two 4-PFA moieties and two oxygen atoms from two nitrate anions; [Zn(4-PFA)(2)(NO(3))(2)] units are linked by hydrogen bonds N-H.O and O-H.O forming one-dimensional chains. Complex 2 is a tetranuclear macrocycle compound consisting of two 4-BPFA moieties and two Hg atoms; [Hg(2)(OAc)(4)(4-BPFA)(2)] units form 1-D chains by hydrogen bonds N-H.O as complex 1. Some complexes with 1,1'-bisubstituted pyridine-containing ferrocene ligands have been described, but their crystal data are limited. Compound 2 is the first example of a macrocyclic pyridine-containing ferrocenyl complex. The third-order nonlinear optical (NLO) properties of 4-PFA, 4-BPFA, and complexes 1-3 were determined by Z-scan techniques. The results indicate that all the compounds exhibit strong self-focusing effect. The hyperpolarizability gamma values are calculated to be in the range 1.51 x 10(-)(28) to 3.12 x 10(-)(28) esu. The gamma values are nearly twice as large for complexes 1-3 as for their individual ligands, showing that the optical nonlinearity of the complexes is dominated by the ligands.     

Synthesis,crystal structure,and properties of a new lanthanide tartrate coordination polymer

A new coordination polymer of terbium tartrate [Tb(H₂O)₃(C₄H₅O₆)(C₄H₄O₆)] has been synthesized and crystallizes in the polar space group P4₁ with cell constants a = 6.0415(9), b = 6.0415(9), c = 36.516(7) Å, V = 1332.8(4) ų, Z = 4. The terbium(III) ion of title complex is nine-coordinate through oxygen donors. Four different coordination modes of tartrate occur. This Tb(III) complex exhibits a characteristic luminescence in the visible region upon excitation at 353 nm. The temperature-dependent magnetic properties of the Tb(III) complex were investigated in the temperature range of 2–300 K. Title compound exhibits significant ferroelectric properties at room temperature (remnant polarization 2P _r = 0.160 μC cm^?2, coercive field 2E _c = 44.5 kV cm^?1, saturation of the spontaneous polarization P _s = 0.176 μC cm^?2).     

Synthesis,structure and properties of a one-dimensional coordination polymer containing both dicyanamide and ethylenediamine

The nickel(II) complex [Ni(en)₂{N(CN)₂}]ClO₄ 1 (en?=?ethylenediamine) has been synthesized and its structure determined. The complex forms a one-dimensional chain structure via the bidentate bridging ligand dicyanamide. A two-dimensional network is formed via interchain hydrogen-bond interactions. The magnetic properties of the compound (5–300?K) show the existence of weak antiferromagnetic exchange interactions between paramagnetic centers along chains.     

Synthesis,crystal structure and magnetic properties of a two-dimensional lamellar coordination polymer manganese(II) pyrazinecarboxylate

The two-dimensional (2D) lamellar coordination polymer [Mn(pzc)₂] _n (pzc = pyrazinecarboxylate) was prepared and its structure determined by X-ray diffraction. Each Mn^II ion lies in a distorted octahedron coordination sphere, and the pzc ligand adopts two types of bridging mode. As a result, there are two different distances between adjacent Mn^II atoms: one being 3.50(6) Å via ₂-O forming a dimer of Mn^II, and the other 5.65(4) Å through the syn–anti carboxy oxygen atoms. The latter links the dimer to form an extended 2D lamellar structure. All Mn^II ions in each layer are nearly coplanar. The adjacent sheets are significantly associated via hydrogen bonding and the shortest interlayer Mn·Mn separation is 9.4 Å. The e.s.r. spectrum shows a broad isotropic band centered at g = 2.019. Temperature-dependent magnetic susceptibility measurements (2.0–300 K) reveal the presence of an antiferromagnetic interaction in the coordination polymer.     

Synthesis,crystal structures,and thermal and thermodynamic properties of dimorphic copper(I) coordination polymers

A second modification of the literature-known copper(I) coordination polymer CuCl(pyridazine) was prepared by the reaction of CuCl with pyridazine in acetonitrile. The crystal structure of catena[CuCl(mu(2)-pyridazine-N,N)] is built up of CuCl chains of which each two are connected by the pyridazine ligands to form double chains that are directed parallel to the crystallographic a-axis. In the literature known form LI (CuCl)(2) dimers occur that are connected to chains by the pyridazine ligand. On heating, compound I and LI lose half of the pyridazine ligands and transform to the new 2:1 coordination polymer poly[(CuCl)(2)(pyridazine-N,N)] (II), which transforms at higher temperatures to CuCl. The crystal structure of II is composed of discrete CuCl tetra-chains that are linked by the pyridazine ligands to sheets parallel to (010). The same thermal reactivity is found for the literature-known compound CuBr(pyridazine) (LII), which is isotypic to LI. On heating LII a transformation into the new 2:1 compound poly[(CuBr)(2)(pyridazine-N,N)] (III) is observed, which is isotypic to II. The thermal reactivity of all compounds and the transformation behavior as well as the range of thermodynamic stability of the dimorphic modifications were studied using DTA-TG-MS and DSC measurements, temperature dependent X-ray powder investigations, and crystallization experiments.     

Synthesis,characterisation and crystal structure of a cobalt(II)-hexamethylenetetramine coordination polymer

A novel one-dimensional zigzag coordination polymer, dinitrodiaqua-bis(hexamethylenetetramine)cobalt(II) was synthesised and characterised, and the structure was determined by single-crystal X-ray diffraction. The compound has a chain structure with each cobalt atom covalently bonded to two nitrate ions, two water molecules and two HMTA molecules, giving a slightly distorted octahedral geometry about the cobalt atom. Each HMTA ligand uses two of its N atoms to bond to two cobalt atoms giving an approximately bent Co–HMTA–Co configuration. Each chain is hydrogen bonded through OH···N and OH···O interactions with neighbouring chains leading to an overall polymer structure. Thermal studies show significant mass loss corresponding to the loss of the coordinated water molecules and the decomposition of both the nitrate ions and the HMTA.     

一种锰的超分子化合物的制备、结构及非线性光学 性质研究

用MnSO4·H2O,KSCN,六次甲基四胺(HMTA)制备出超分子化合物[Mn(NCS)2(H2O)2(HMTA)2][Mn(NCS)2(H2O)4](H2O)2,并测定了其晶体结构。该化合物由[Mn(NCS)2(H2O)2(HMTA)2],[Mn(NCS)2(H2O)4]和H2O三部分组成,每一个HMTA配体中仅有一个N原子与Mn原子配位,剩余的3个N分别与[Mn(NCS)2(H2O)4]中的H2O及结晶H2O之间形成氢键。[Mn(NCS)2(H2O)2(HMTA)2]和[Mn(NCS)2(H2O)4]之间通过N…H—O氢键边接成无限延伸的线性长链,链与链、以及链和结晶H2O之间通过七种形式的氢键构成三维结构的超分子。用Z-扫描法测定该化合物在DMF溶液中的三阶非线性光学性质,发现它具有自聚焦效应,三阶非线性折射系数n2=9.52×10^-9m^2·W^-1,非线性极化率χ^(3)=3.41×10^-12esu.     

Synthesis,crystal structure,and properties of a three-dimensional coordination polymer [Cd(PMP)2] n

A new Cd(II) coordination polymer, [Cd(PMP)₂] _n (1) [PMP = 1-phenyl-3-methyl-5-pyrazolone], has been synthesized by the reaction of Cd(CH₃COO)₂·2H₂O with PMP and characterized by elemental analysis, IR spectrum, fluorescence spectrum, UV–vis spectrum, TG–DTA, and electrochemical analysis. Single crystal X-ray diffraction reveals that the complex has a three-dimensional network. Each PMP acts as bidentate bridging ligand and each Cd(II) center is surrounded by two O atoms and two N atoms from four different PMP ligands to form distorted tetrahedral coordination geometry. The photoluminescence study shows the complex exhibited strong solid state blue fluorescent emission at room temperature, and the TG–DTA analysis demonstrated that it has highly thermal stability. Furthermore, the electrochemical property of the complex has been investigated for the first time in DMF by cyclic voltammetry, and the results showed that it has an irreversible process.     

肼基硫代甲酸酯配合物的合成、晶体结构、光谱及三阶非线性光 学性质研究

报道三种有推拉电子基团的肼基硫代酸酯衍生物配体(HL^1^～^3)。此类配体与二价过渡金属离子配位时脱去一质子,形成D-M-D和A-M-A(D=给体,M=金属,A=受体)类型、含有共轭体系的中性配合物。本文集中研究了该类配体的镍、铜、钯、铂配合物的IR、磁化率、ESR谱,电子光谱和三阶非线性光学性质,通过光谱研究初步确定了它们均为平面正方形构型配合物,文中还报道了CuL2^1的晶体结构。晶体属P1空间群,a=0.7835(2),b=1.0530(2),c=1.1816(2)nm,α=100.61(3),β=92.38(3),γ=110.00(3)ⅲ,Z=1,最终的R因子为0.063。通过晶体结构测试,进一步确定铜配合物的结构为平面构型。     

Synthesis,crystal structure and magnetic properties of 2D bi-layered coordination polymer

A new coordination polymer, [Ni(pydc)(H₂O)₂]?·?H₂O (1) (H₂pydc?=?pyridine-3,4-dicarboxylic acid), have been synthesized by treating Ni(II) nitrate with 3,4-pyridinedicarboxylic acid under hydrothermal conditions. The single-crystal X-ray structure reveals that 1 is a 2D bi-layered coordination polymer. Single-crystals are triclinic, space group P 1 , with a?=?7.065(3), b?=?7.812(4), c?=?9.031(4)?Å, α?=?75.568(8), β?=?68.970(8), γ?=?75.927(8)°, V?=?444.0(3)?ų, Z?=?2. Variable temperature magnetic susceptibility measurements demonstrate a ferromagnetic interaction in 1.     

Synthesis,crystal structure,and DNA-binding studies of a one-dimensional copper(II) polymer bridged both by oxamidate and thiocyanato ligands

A new one-dimensional copper(II) polymer, [Cu₄(dmapox)₂(SCN)₄(CH₃OH)₂] _n , where dmapox is the dianion of N,N′-bis[3-(dimethylamino)propyl]oxamide, was synthesized and characterized by elemental analysis, conductivity measurement, IR, and electronic spectral studies. The crystal structure of the copper(II) complex has been determined by X-ray single-crystal diffraction. The complex crystallizes in triclinic, space group P ? 1 and exhibits infinite one-dimensional copper(II) polymeric chain bridged both by bis-tridentate μ-trans-dmapox and μ-1,3-thiocyanato ligand. The environment around the copper(II) atom can be described as distorted square-pyramid. The Cu···Cu separations through the oxamidate and thiocyanato bridges are 5.246(2) Å (Cu1–Cu1ⁱ), 5.2649(14) Å (Cu2–Cu2ⁱⁱ), and 5.8169(15) Å (Cu1–Cu2), respectively. The interaction of the copper(II) complex with herring sperm DNA (HS-DNA) has been investigated by using absorption and emission spectral and electrochemical techniques and viscometry. The results reveal that the copper(II) complex may interact with DNA in the mode of groove binding with the intrinsic binding constant of 2.56 × 10⁵ M^?1.     

三维氰基桥联Cu(I)配位聚合物的模板合成和晶体结构

将(Et4N)3Mn(CN)6和Cu(en)2(ClO4)2反应得到了三维配位聚合物{[Cu(Ⅱ)(en)2*H2O][Cu(I)2(CN)4]}n(en＝乙二胺),用元素分析、ICP分析、IR光谱对配合物进行了表征.X-射线衍射结果表明晶体属单斜晶系,空间群为Cc(#9),晶胞参数a＝14.759(3),b＝7.734(2),c＝14.247(3)(A),β＝112.65(3)°,V＝1500.9(5)(A)3,Z＝4,Dc＝1.916Mg*m-3,F(000)＝868,最终偏离因子R1＝0.0267,wR2＝0.0633.该配合物结构中Cu(I)离子间通过氰基桥联形成三维峰窝样主体骨架结构,而Cu(Ⅱ)配离子[Cu(en)2*H2O]2+被包合在主体内架通道空腔的中央.该配合物的合成是利用[Cu(CN)2]-为建筑砖块,[Cu(en)2*H2O]2+为模板的自组装反应.     

酞菁和酞菁铜的三阶非线性光学性质

用INDO/SDCI方法研究了酞菁和酞菁铜的电子结构, 紫外-可见光谱, 三阶非线性光学系数及其色散效应, 发现酞菁铜中Cu^2+对γ的贡献很小, 故酞菁与酞菁铜的γ几乎相等, 我们的计算结果对此进行了合理的解释。     

Hydrothermal synthesis,crystal structure and third-order non-linear optical property of a copper chloride cluster

A novel one-dimensional chain coordination polymer [[CuCl₂]₂(phen)₂]_∞ (1) and a three-dimensional coordination polymer [[CuCl] (phen)₂](CuCl₂) (2) were synthesized from simple hydrothermal reactions and the structures were characterized with elemental analysis, FT-IR spectrum and X-ray diffraction. Compound 1 crystallized in the monoclinic space group Cc with a?=?9.874(2), b?=?17.871(4), and c?=?13.440(3)?Å, α?=?90.00°, β?=?106.59(3)°, γ?=?90.00°, R ₁?=?0.0463, wR ₂?=?0.0819. Compound 2 crystallized in the monoclinic space group P2/c with a?=?14.4084(13), b?=?12.6280(11) and c?=?13.3560(12)?Å, α?=?90.00°, β?=?111.490(2)°, γ?=?90.00°, R ₁?=?0.0771, wR ₂?=?0.1439. In the packing structure, π–π stacking interactions are the most significant factors controlling the novel supramolecular sheets for the title compound. Moreover, the third-order non-linear optical property of the two compounds were also investigated and they show reverse saturable absorption and self-focusing performance.