Hydrothermal Syntheses, Supramolecular Structures and the Third-order Non-linear Optical Properties of Three Copper(I) Halide Amine Complexes Connected via Secondary Bonding Interactions

ＩｎｔｒｏｄｕｃｔｉｏｎＳｅｃｏｎｄａｒｙｂｏｎｄｉｎｇｓｓｕｃｈａｓｈｙｄｒｏｇｅｎｂｏｎｄｓａｎｄπ πｉｎｔｅｒａｃｔｉｏｎｓａｒｅｉｍｐｏｒｔａｎｔｎｏｎ ｃｏｖａｌｅｎｔｉｎｔｅｒｍｏｌｅｃｕｌａｒｆｏｒｃｅｓ ,1ｗｈｉｃｈｃｏｎｔｒｉｂｕｔｅｔｏｓｅｌｆ ａｓｓｅｍｂｌｙｐｒｏｃｅｓｓｅｓｗｈｅｎｅｘｔｅｎｄｅｄｓｔｒｕｃｔｕｒｅｓａｒｅｆｏｒｍｅｄｆｒｏｍｓｉｍｐｌｅｐｒｅｃｕｒｓｏｒｓ .Ｒｅｃｅｎｔｌｙｍｕｃｈａｔｔｅｎｔｉｏｎｈａｓｂｅｅｎｐａｉｄｔｏｔｈｅｈｙｄｒｏｇｅｎｂｏｎｄ…     

Hydrothermal Synthesis and Characterization of a One—Dimen—sional Copper（Ⅰ） Halide Cluster with 1,10—Phenanthroline

The title compound Cu₂Cl₂phen (phen = 1,10‐phenanthroline, C₁₂H₈N₂) 1 was synthesized from CuCl₂·2H₂O, CuCl and phen by hydrothermal method and its structure was determined by single crystal X‐ray analysis. With phen, CuG forms one‐dimensional chains, which comprise two zigzag chains based on fused Cu‐X units and connected via covalent bonds. The compound contains two crystallographically unique monovalent copper ions, Cu(1) and Cu(2). The Cu(1) atom in the tetrahedral site, is coordinated to two bridging Cl^? and two N atoms in phen. The Cu(2) atom with a slightly distorted triangular planar geometry, is coordinated to three Cl^?. The compound 1 was crystallized in monoclinic, space group P2₁/n with a = 0.37338(4), b = 1.9510(2), c = 1.68008(19) nm, β = 95.605 (3)°, R = 0.0458, and was characterized by elemental analysis, IR spectrum and TGA analysis.     

Hydrothermal Syntheses and Crystal Structures of Cobalt（Ⅱ） Complexes Constructed by Dipyrido[3,2-a：2＇,3＇-c]phenazine and Different Carboxylate Ligands

Two new metal-organic complexes,{[Co2(bptc)(DPPZ)2(H2O)2]·H2O}n 1 and {[Co2(ccm)2(DPPZ)2]·2H2O}n 2,were obtained by the hydrothermal reactions of Co(NO3)2·6H2O with chelating ligand dipyrido[3,2-a:2',3'-c]phenazine(DPPZ) and the corresponding carboxylic acid,namely,3,3',4,4'-benzophenonetetracarboxylic acid(H4bptc) or 2-carboxycinnamic acid(H2ccm),respectively.The complexes were structurally characterized by single-crystal X-ray diffraction,elemental analyses,IR spectra,and thermal gravimetry.1 presents unique chiral chain structures,which are further consolidated into three-dimensional supramolecular frameworks via noncovalent bonds,such as hydrogen bonding and π-π interactions.2 features infinite double-chain structures,which are connected by strong π-π interactions to result in three-dimensional supramolecular architectures.     

Syntheses,Crystal Structures and Electrochemical Properties of Supramolecular Complexes [M4L12]·（HPO4）·（PO4）2（L=2,2＇-Dibenzimidazole,M=Co and Ni）

Two novel supramolecular complexes,[M4L12]·(HPO4)·(PO4)2(L = 2,2'-dibenzi-midazole,M = Co and Ni) were synthesized by the hydrothermal method and characterized by elemental analysis,IR,UV,and TG-TGA,and the crystal structures were determined by single-crystal X-ray diffraction.The results showed that both of them belong to the cubic system and space group I 4 3d.Crystal parameters of C168H121Co4N48O12P3(1):a = b = c = 2.5104(6) nm,V = 15.820(7) nm3,Mr = 3332.75,Z = 4,Dc = 1.399 Mg/m3,μ = 0.521 mm-1,F(000) = 6852,S = 1.011,the final R = 0.0248 and wR = 0.0663 for 2120 observed reflections(I > 2σ(I)) and R = 0.0315 and wR = 0.0706 for all data.Crystal parameters of C168H121Ni4N48O12P3(2):a = b = c = 2.4977(5) nm,V = 15.581(5) nm3,Mr = 3331.87,Z = 4,Dc = 1.420 Mg/m3,μ = 0.587 mm-1,F(000) = 6868,S = 1.074,the final R = 0.0443 and wR = 0.1364 for 1774 observer reflections(I > 2σ(I)) and R = 0.0647 and wR = 0.1492 for all data.Each of them consisted of four M(II) cations,twelve 2,2'-dibenzimidazole ligands,one monohydrogen phosphate anion and two phosphate anions in the single cell.The central M(II) cation,coordinated with six alkaline nitrogen atoms from three 2,2'-dibenzimidazole ligands,displayed the expected distorted-octahedral geometry.The 3D supramolecular system was formed by the hydrogen bond N-H...O and π-π stacking interaction between neighboring single cells.Complex 1 showed two irreversible single-electron reduction processes of the central metal ion at-0.06 and-0.42 V in DMF solution.     

Hydrothermal Synthesis and Characterization of a One-Dimensional Copper(I) Halide Cluster with 1,10-Phenanthroline

ＩｎｔｒｏｄｕｃｔｉｏｎＣｏｐｐｅｒ(Ｉ)ｈａｌｉｄｅｓｃａｎｆｏｒｍｏｌｉｇｏｍｅｒｉｃ (ｎｏｒｍａｌｌｙｄｉｍｅｒｓｏｒｔｅｔｒａｍｅｒｓ)ａｎｄｐｏｌｙｍｅｒｉｃｆｒａｍｅｗｏｒｋｓｔｈｅｍ ｓｅｌｖｅｓ .Ａｌｌｔｈｅｃｏｐｐｅｒ(Ｉ)ｈａｌｉｄｅｐｏｌｙｍｅｒｉｃｓｐｅｃｉｅｓａｒｅｂａｓｅｄｏｎｏｎｅ ｄｉｍｅｎｓｉｏｎａｌｃｈａｉｎｓ ,ｎｏｅｘａｍｐｌｅｓｏｆｔｗｏ ｄｉ ｍｅｎｓｉｏｎａｌｓｈｅｅｔｓｈａｖｅｂｅｅｎｆｏｕｎｄｓｏｆａｒ .Ｉｎｏｒｄｅｒｔｏｉｎ ｃｒｅａｓｅｔｈｅｄｉｍｅｎｓ…     

A New Copper(I) Complex Based on Imidazole and Triphenylphosphine Ligands: Synthesis,Structure, Third‐Order NLO,and Fluorescence Properties

A new candidate [Cu(PPh₃)₂Him]Br ( 1 , PPh₃=triphenylphosphine, Him=1‐H‐imidazole) for nonlinear optical (NLO) materials has been synthesized and characterized crystallographically. The third‐order NLO optical properties were measured by the Z‐scan technique with an 8 ns pulsed laser at 532 nm. Compound 1 exhibits strong NLO absorptive abilities [α₂=(61±5)×10^?12] and effective self‐focusing performance [n₂=(15±3)×10^?18 m²·W^?1] in 1.01×10^?4 mol·dm^?3 DMF solution. The compound also exhibits luminescence in DMF solution at room temperature and shows narrow emission with maximum at 382 nm. The electronic structure and photoluminescent process were investigated by means of TD‐DFT calculations. The results suggest that the contribution to the frontier orbitals from the Cu? Br δ bond plays a crucial role in its linear optical properties, and the origin of luminescence is attributable to the π??→n transitions.     

Investigation of Copper Halide:Hydrothermal Syntheses and Characterization of CuBr2(C12H8N2) and Cu3Br3(C12H8N2)2

The reaction of CuBr₂ with 1,10‐phen‐H₂O (1,10‐phen = 1,10‐phenanthroline) gave two compounds: CuBr₂(C₁₂H₈N₂) and Cu₃Br₃(C₁₂H₈N₂)₂. Their structures have been characterized by single‐crystal X‐ray diffraction analysis, elemental analyses, thermogravimetric analyses (TGA) and measurement of variable temperature magnetic susceptibility. Crystal data for CuBr₂(C₁₂‐H₈N₂): monoclinic, space group P2₁/n, a = 0.9977(3) nm, b = 0.65138(14) nm, c = 1.8207(4) nm, β = 91.624(18)°, V = 1.1828(5) nm³, Z = 2. Crystal data for Cu₃Br₃(C₁₂H₈N₂)₂: monoclinic, space group C2/c, a = 1.00167(11) nm, b = 1.4523(4) nm, c = 1.6295(3) nm, β = 94.386(14)°, V = 2.3635(8) nm³, Z = 3.     

由大茴香酸与含氮杂环配体构筑的锌、铜配合物的水热合成、晶体结构与荧光性质

通过水热法,以大茴香酸（Hmba=methoxybenzoic acid）、2,2’-联吡啶（bipy）为配体,合成了2个配合物：[Zn（mba）（bipy）（HCOO）]_n（1）和[Cu（mba）（bipy）₂]·2Hmba（2）,对其进行了红外光谱、热重分析、单晶X射线衍射和荧光光谱等分析。配合物1属单斜晶系,空间群为P2/c,Zn（Ⅱ）离子处在五配位的变形三角双锥环境中。每个HCOO-桥联2个相邻Zn（Ⅱ）离子,形成一维链,然后通过氢键作用和芳环间的π-π堆积延伸一维链为三维网络超分子结构。配合物2属三斜晶系,空间群为P1,Cu（Ⅱ）离子与配位原子构成五配位的变形三角双锥结构。其配合物单元通过芳环间的π-π堆积作用连接为一维超分子链,一维链通过氢键、芳环间的π-π堆积和C-H…π相互作用拓展为三维超分子结构。荧光光谱研究表明,配合物1在327 nm（λ_max）处具有强的荧光发射。     

由大茴香酸与含氮杂环配体构筑的锌、铜配合物的水热合成、晶体结构与荧光性质

通过水热法,以大茴香酸(Hmba=methoxybenzoic acid)、2,2′-联吡啶(bipy)为配体,合成了2个配合物:[Zn(mba)(bipy)(HCOO)]n(1)和[Cu(mba)(bipy)2]·2Hmba(2),对其进行了红外光谱、热重分析、单晶X射线衍射和荧光光谱等分析。配合物1属单斜晶系,空间群为P2/c,Zn(Ⅱ)离子处在五配位的变形三角双锥环境中。每个HCOO-桥联2个相邻Zn(Ⅱ)离子,形成一维链,然后通过氢键作用和芳环间的π-π堆积延伸一维链为三维网络超分子结构。配合物2属三斜晶系,空间群为P1,Cu(Ⅱ)离子与配位原子构成五配位的变形三角双锥结构。其配合物单元通过芳环间的π-π堆积作用连接为一维超分子链,一维链通过氢键、芳环间的π-π堆积和C-H…π相互作用拓展为三维超分子结构。荧光光谱研究表明,配合物1在327 nm(λmax)处具有强的荧光发射。     

Electronic Structures of Asymmetrically Substituted Phthalocyanines and Their Second Non‐linear Optical Properties

Quantum‐chemical AM1 calculations were performed to study the geometries, the electronic structures and the second nonlinear optical properties of phthalocyanine and some asymmetrically substituted phthalocyanines, which include tert‐butyl, amino, dimethylamino, nitro, fluoro, chloro, bromo, iodo and nitrile substituents. The relationships of the second nonlinear optical coefficients β with dipole moment μ, and β with the energy‐gap differences of frontier orbitals ΔE_DA were discussed. Two relationships are regular and all ΔE_DA ‐ μ show very good linear relationship.     

Luminescent Property of a Supramolecular Silver(I)‐Thiolate Complex Based on Secondary Ag‐S Interactions and Hydrogen Bonds

The supramolecular silver(I)‐thiolate complex [Ag(μ₂‐SC₄N₂H₄)₂(SCN)]_n has been prepared from the reaction of AgSCN and pyrimidine‐2‐thiol in DMF. X‐ray diffraction analysis shows that the supramolecular structure exhibits one‐dimensional chain through the secondary Ag‐S interactions and the chains are further linked by strong hydrogen bonds to form a three dimensional network. The luminescence effect from the silver‐centered state of S→Ag LMCT in solid state is different from that in solution due to the secondary Ag‐S interactions.     

羧酸铜与单螺旋吡啶胺配体自组装的两种新型超分子配合物

Two novel supramolecular complexes [Cu（bpapa）（dhbd）]·CHaOH （1） and [Cu（bpapa）（ma）]·ma （2） （bpapa= bis[6-（2-pyridylamino）pyrid-2-yl]amine, dhbd=2,3-dihydroxybutanedioate dianion, ma=a-methacrylate） were rationally designed, synthesized and characterized by single crystal X-ray diffraction, IR, electronic spectroscopy and thermogravimetric analyses. Complex 1 was the first oligo-a-pyfidylamino complex based on hydroxypolycarboxylate and self-assembled into a 3D honeycomb configuration network with open channels and tubes containing 1D ladder-shaped double chains formed by hydrogen bonds and aromatic π-π stacking interactions. Complex 2 constructed a 2D supramolecular network extended by 1D chains from dimeric supramolecular synthon through noncovalent supramolecular interactions. In the two complexes, the chelating monohelical ligand adopted all-anti configuration. Density functional theory calculations were applied to 1 and 2.