Solvothermal Synthesis of New Luminescent Zinc(II) Coordination Polymers with One‐Dimensional Homochiral Structures

By using a dual‐ligand approach, two new homochiral zinc(II) coordination polymers, Zn₂(phen)₂(H₂O)₂(cam)₂ · ethanol ( 1 ) and Zn(bipy)(cam) ( 2 ) [phen = 1,10‐phenanthroline, bipy = 2,2′‐bipyridine, H₂cam = (1R,3S)‐(+)‐camphoric acid] have been synthesized under solvothermal conditions. Compound 1 has a zigzag chain‐like structure and compound 2 has a linear chain‐like structure. The two compounds exhibit intense photoluminescence upon photoexcitation at 280 and 290 nm, respectively.     

Solvothermal Synthesis,Crystal Structure,and Strong Luminescence of the First Organic‐Templated Europium Sulfate Chloride

The first organic amine templated europium sulfate chloride [C₆N₄H₂₂]_0.5Cl[Eu(SO₄)₂ · H₂O] ( 1 ) was synthesized solvothermally and structurally characterized by single‐crystal X‐ray diffraction, IR spectroscopy, TGA, and ICP. Crystal analyses of compound 1 shows a novel inorganic layer constructed from [–Eu–O–S–O–]_n chains. The adjacent chains are connected by sharing the bridging SO₄^2– groups to generate eight‐membered rings. The very strong luminescence in the red light region indicates compound 1 is an excellent candidate for red fluorescent materials.     

Solvothermal Synthesis,Crystal Structure,and Properties of a New Organic‐Templated Holmium Sulfate with 1D Single Ladder Chains

A new organic amine templated 1D holmium sulfate (C₂H₈N)[Ho(SO₄)₂ · H₂O] ( 1 ) has been synthesized and solvothermally and structurally characterized by single‐crystal X‐ray diffraction, IR spectroscopy, thermogravimetric and X‐ray diffraction analyses as well as scanning electron microscopy (SEM). The structure of framework 1 is constructed from HoO₈ polyhedra and SO₄ tetrahedra. S(1) and S(2) connects Ho(1) and its crystallographic partners by using three S–O–Ho linkages to generate double chains, whereas the adjacent double chain are connected by μ₃‐O (O₅) atoms to form a novel single ladder chains.     

Synthesis,Crystal Structures,and Magnetic Properties of Three New Iron Complexes Derived from 3,5‐Bis(pyridin‐2‐yl)‐1,2,4‐triazole

Two new iron(III) complexes and one iron(II) complex have been synthesized from the solvothermal reactions of FeCl₃·6H₂O with 3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole (Hbpt) in methanol or acetonitrile. KSCN acted as the reducing agent in the synthesis of iron(II) complex of 3 . [FeCl₃(Hbpt)(H₂O)]·H₂O ( 1 ) crystallizes in the triclinic space group with a = 7.475(1), b = 9.468(2), c = 12.309(2) Å, α = 73.880(2), β = 74.746(2), γ = 81.849(2)°, V = 805.2(2) ų, Z = 2. [Fe₂(bpt)₂Cl₄] ( 2 ): orthorhombic space group Pnnm with a = 9.895(2), b = 10.632(2), c = 13.195(2) Å, V = 1388.1(4) ų, Z = 2. [Fe₂(bpt)₂(MeOH)₂Cl₂] ( 3 ): orthorhombic space group Pbca with a = 14.4204(16), b = 9.8737(11), c = 19.792(2) Å, V = 2818.1(5) ų, Z = 4. 1 features the first structurally characterized metal complex of the neutral Hbpt ligand in which the Hbpt ligand adopts an unprecedented zwitterionic form. 2 shows a neutral dinuclear iron(III) complex and the [Fe₂(bpt)₂]⁴⁺ unit is ideally planar. The two iron(III) ions separated by a distance of 4.408(2) Å are doubly triazolate‐bridged. Each dimeric unit is connected with six other dimeric ones via the bifurcated C‐H···Cl hydrogen bonds, these connections extend the dimeric moieties into a three‐dimensional molecular architecture. 3 is a neutral centrosymmetric dinuclear Fe^II complex, in which intermolecular moderate O‐H···N hydrogen bonding interactions between the methanol molecules and 4‐position nitrogen atoms of the triazolato groups extend the dinuclear species into a two‐dimensional supramolecular architecture of (4,4) topology. Magnetic studies indicate there exists an antiferromagnetic spin coupling in Fe^III₂ and Fe^II₂ units via the double triazolate bridges in 2 and 3 .     

On the Crystal Structure of a Previously Unknown Anhydrous Zinc Hydroxide Sulfate

Anhydrous zinc hydroxide sulfates are promising precursors for the preparation of pigments and ZnO nanomaterials. The crystal structure of one such compound 5[Zn(OH)₂] · 2[ZnSO₄] was determined from high resolution laboratory X‐ray powder diffraction data by use of a combination of charge flipping, 18 simulated annealing, 26 and difference Fourier analysis. The material crystallizes in the space group P$\bar{1}$ with the lattice parameters of a = 5.4559(2) Å, b = 8.0528(3) Å, c = 8.9275(3) Å, α = 112.697(2)°, β = 85.219(3)°, γ = 95.441(3)°, and a volume of V = 359.76(2) ų. The basic crystal structure consists of brucite type Zn(OH)₂ layers where every sixth octahedral site is vacant. Tetrahedrally coordinated zinc ions are located above and below these vacancies and consecutive layers are bridged by sulfate molecules. The composition of this layered structure can be written as [Zn₅^VI□(OH)₄ · Zn₂^IV(OH)₆ · (SO₄)₂]. Its thermal decomposition was studied by X‐ray powder diffraction and thermal analysis.     

Synthesis,Crystal Structure,and Photocatalytic Properties of a Zinc(II) Coordination Polymer Based on 3‐Hydroxy‐2‐pyridinecarboxylic Acid

The zinc(II) compound, [Zn₃(HL)₆]_n ( 1 ) (H₂L = 3‐hydroxypyridine‐2‐carboxylic acid) was synthesized by a solvothermal reaction of Zn(NO₃)₂ · 6H₂O and 3‐hydroxypyridine‐2‐carboxylic acid as raw materials. The structure of complex 1 was determined by single‐crystal X‐ray diffraction analysis and further characterized by elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, as well as powder X‐ray diffraction. X‐ray structure analysis demonstrates that the complex crystallizes in the monoclinic system, space group P2₁/n. There are three zinc ions in the asymmetric unit, which are either five‐coordinate or six‐coordinate. The asymmetric units are further bridged by the carboxylate of the organic ligands, featuring a 2D framework. The solid state diffuse‐reflectance UV/Vis spectra reveals that complex 1 has semiconducting nature with the energy bandgap (E_g) estimated to be 3.11 eV. The photocatalytic properties of complex 1 in degradation of organic dyes were further investigated. Results showed that the complex could degrade 54 % of the dye methylene blue solution within 120 min under UV irradiation light and reused for five times without the decline of the photocatalytic activity.     

具有五配位Zn中心的微孔金属有机双桥连配体化合物的溶热合成及表征

A new two dimensional zinc complex was reported. This compound was synthesized under solvothermal condition by using THF as solvent. The crystal structure was determined by using single crystal X-ray diffraction. Crystal data: Zr', (B DC)( D ABCO)( H 20)z, monoclinic, space group C 2/c,a =10.871(17),b=19.10 (3),c=7.15 5(川,a= 90,口二115.99(3),Y=90,Z 二8,V 二1335(4),Dr二2.085岁cm3,R二0.08 58. This compound has two-dimensional network structure. Each zinc metal center was coordinated by two DABCO, two BDC and one water molecule. DABCO and BDC ligands bridge to two zinc atoms, respectively. The extension of this〔。-ordination result in a two-dimensional network and form a 7.16 x 9.98A zporous structure. It was interesting to find that the 2-dimensional was an interpenetrated structure formed by two coordinate polymer networks. This kind of structure is very rare in the coordinate compounds. The m-m interaction between the phenyl group of BDC was believed to the key of the growth of this coordination network.     

On the Flexibility of Thioantimonate Networks: Solvothermal Syntheses and Crystal Structures of Six New Thioantimonates(III) with the [Sb4S7]2− Anion

Six new thioantimonates(III) with the [Sb₄S₇]²⁻ anion were obtained under solvothermal conditions with in‐situ formed transition metal complexes as structure directors. In the two isostructural compounds [Fe(dien)₂]Sb₄S₇·H₂O ( 1 ) and [Co(dien)₂]Sb₄S₇·0.5 H₂O ( 2 ) (dien = diethylenetriamine; space group: P2₁/c) the layered [Sb₄S₇]²⁻ anion is characterized by Sb₈S₈ rings with a diameter of about 9.6·7.6Å. The cation complexes are located above and below the pores of the rings. Despite the larger size of the cation complex the network topology of the third thioantimonate [Ni(dien)(tren)]Sb₄S₇ ( 3 ) (tren = tris(2‐aminoethyl)amine; space group: P2₁/n) is similar to that of the first two compounds. In the isostructural thioantimonates [M(trien)]Sb₄S₇ (M = Zn ( 4 ); M = Mn ( 5 ); trien = triethylenetetramine; space group: ) the M²⁺ ions are fivefold coordinated by four N atoms of the amine molecule and by one S atom of the thioantimonate anion forming a MN₄S trigonal bipyramid. Sb₈S₁₆ building blocks are the central structural motifs of the anion. Two of the terminal S atoms at the periphery of the Sb₈S₁₆ units are bound to M²⁺ ions and the four remaining terminal S atoms connect adjacent Sb₈S₁₆ groups into the final [Sb₄S₇]²⁻ chain. [Ni(tren)]Sb₄S₇ ( 6 ) (space group: ) contains a one‐dimensional anionic chain. The Ni²⁺ ion has two bonds to the [Sb₄S₇]²⁻ anion which is a unique feature in the thioantimonate(III) chemistry. The NiN₄S₂ octahedron is severly distorted with one very long Ni‐S bond of 2.782(2) Å. In all compounds several short S···H distances indicate hydrogen bonding interactions.     

[VO(dien)]2GeS4: Solvothermal Synthesis and Crystal Structure with an Ortho‐Thiogermanate as Tetradentate Ligand

The compound [VO(dien)]₂GeS₄ ( 1 , dien = diethylenetriamine) features an ortho‐thiogermanate anion [GeS₄]^4–, which acts as tetradentate ligand joining [VO(dien)]^2– complexes. The compound was obtained under solvothermal conditions crystallizing in thenon‐centrosymmetric orthorhombic space group Pna2₁ with a =19.8310(11), b = 8.0814(5), c = 12.0889(9) Å, V = 1937.4(2) ų and Z = 4. The V⁴⁺ cations are in a distorted octahedral environment of a tridentate dien molecule, one oxygen atom and two sulfur atoms from the [GeS₄]^4– anion. A three‐dimensional network is generated by hydrogen bonding interactions.     

一种新型磷酸钛大单晶的溶剂热法合成与结构研究

用水热或溶剂热法合成具有一维链状、二维层状及三维微孔结构的新型磷酸盐ＭｅＰＯ4(Ｍｅ =Ａｌ,Ｆｅ,Ｚｎ ,Ｚｒ等 )晶体目前已成为国内外研究的热点[15 ],这主要是由于磷酸盐结构的多样性以及它们在吸附、分离、催化、光学等方面的良好应用[6 ,7].磷酸钛类化合物作为一类具有良好非线性光学特性及氧化催化性能的功能材料 ,正日益受到人们的重视 ,而获得磷酸钛优质大单晶也是研究热点之一 .这类化合物通常易于得到微晶粉末而难于获得大晶体 ,由于缺少单晶结构数据 ,对具有新型结构磷酸钛的研究目前受到一定限制[8,9],尤其是以有机物为模板…     

Oriented Synthesis of One‐Dimensional Polypyrrole Molecule Chains in a Metal‐Organic Framework

We report for the first time the preparation of single polypyrrole (PPy) molecule chains using a “metal‐organic framework” with 1 nm channels as a template. The obtained one‐dimensional (1‐D) PPy has highly structure order and excellent conductivity, which has improved by as much as five orders of magnitude in comparison with that of 2‐D PPy.

     

Synthesis and X‐ray Crystal Structures of Homotrimetallic Zinc Bisureate Complexes

Alkane elimination reactions of the tethered bis(urea) proligand 1,4‐(tBuNHCONH)₂‐C₄H₈ ( 1 ) with ZnR₂ (R = Me, Et, nPr) yielded trimetallic zinc complexes [RZn‐1,4‐(tBuNHCON)₂‐C₄H₈]₂Zn [R = Me ( 2 ), Et ( 3 ), and nPr ( 4 )]. 2 – 4 were characterized by heteronuclear NMR (¹H, ¹³C) and IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction.     

Synthesis,Crystal Structures and Properties of Two New ­Coordination Polymers Constructed from in situ‐generated Pyridyl‐dicarboxylic Acid Ligands

Two novel coordination polymers [Mn₃(EPDA)₂(H₂O)₈ · (ENA) · (ClO₄) · 0.5(HClO₄) · (CH₃OH) · 2(H₂O)]_n ( 1 ) and[Zn(EPDA)(H₂O)]_n ( 2 ) (EPDA = 5‐ethylpyridine‐2, 3‐dicarboxylic acid, ENA = 5‐ethylnicotinate acid) were synthesized and characterized by IR and UV/Vis spectroscopy, elemental analysis, PXRD, TGA, photoluminescence, and single‐crystal X‐ray diffraction. Organic EPDA^2– and ENA^– anions, the decomposition products of ENA‐Pmmi by removing the –Pmmi group under in situ solvothermal conditions, were obtained by performing the reactions of ENA‐Pmmi with Mn^II or Zn^II perchlorate. In complex 1 , the Mn^II ions were bridged by μ₄‐EPDA^2– anions to give a 2D positively charged layer, and the free ENA^– anion and solvent molecules are filled into the gap between the layers through hydrogen bonding interactions to form a sandwich structure. In compound 2 , the μ₃‐EPDA^2– anions bridge divalent Zn²⁺ ions to form a 1D chain, and the ENA^– anions are not involved in stacking interactions but left in the residual solution. In addition, the ENA‐Imoi instead of ENA‐Pmmi, was selected to further investigate this reaction (ENA‐Pmmi and ENA‐Imoi are imazethapyr homologues), and the same experimental results could be obtained.     

AZ91D镁合金上钼改性锌系磷化膜的制备、 结构及性能

采用在磷化液中添加钼酸钠及腐蚀抑制剂的方法, 在AZ91D 镁合金表面上制备了均匀细致的锌系复合磷化膜. 用XRD对膜层的化学组成及结构进行了表征,用SEM和EDS对膜层的形貌和组分含量进行分析. 结果表明, 磷化膜主要由Zn3(PO4)2·4H2O和单质Zn组成. 在磷化液中加入钼酸钠使磷化膜组织更加细致而且无裂纹. 磷化液中的钼酸钠含量为1.5 g/L时, 磷化膜的结晶最致密, 单质锌的含量最高, 耐蚀性最好. 还提出了一种快速测量镁合金表面膜层耐蚀性的试验方法, 同时对镁合金上的磷化反应的机理进行了探讨.     

Synthesis and Characterization of an Inorganic‐Organic Hybrid Layered Zinc Phosphite [(C2H3N3)Zn(HPO3)]

A inorganic‐organic hybrid zinc phosphite (C₂H₃N₃)Zn(HPO₃) ( 1 ) has been prepared under solvothermal conditions in the presence of 1,2,4‐triazole (trz) ligand.Its structure was determined by single‐crystal X‐ray diffraction, and further characterized by powder X‐ray diffraction (XRD), FTIR spectroscopy, elemental analysis, ICP analysis, thermogravimetric analysis and fluorescent spectrum. It crystallizes in the monoclinic system, space group P2₁/n, a = 7.5515(6) Å, b = 9.1813(8) Å, c = 10.0125(8) Å, β = 111.267(1)°, V = 646.92(9) ų, Z = 4. The structure consists of left‐handed and right‐handed helical chains that are connected through bridging oxygen atoms to form a two‐dimensional layer structure with 4.8‐net. The compound exhibits intense photoluminescence upon photo‐excitation at 326 nm.     

Synthesis of Highly Dispersed Fe3O4 Submicrometer Spheres in a One‐Pot Anion‐induced Solvothermal System

A facile, anion‐induced, one‐pot solvothermal method was successfully developed to prepare two kinds of highly dispersed magnetic Fe₃O₄ submicrometer spheres at 200°C in 12 h. The diameters of the as‐prepared Fe₃O₄ submicrometer spheres are ~500 and ~200 nm, respectively. With the guidance of OAc ⁻ ions, the size and morphology of the Fe₃O₄ spheres could be well controlled. The saturation magnetization of the Fe₃O₄ spheres was measured to be 84 and 74 emu/g, respectively. The assembly of tiny precursor nuclei into the Fe₃O₄ spheres relies on Ostwald ripening. The synthesized Fe₃O₄ submicrometer spheres show good magnetic response, good water solubility, and uniform size.     

Solvent Molecule Controlled Zinc(II) Metal‐Organic Frameworks with Different Topology

Two zinc(II) coordination polymers, namely [Zn₂(bptc)(DMF)₂(H₂O)]_n ( 1 ) and [Zn(bptc)_0.5(DMA)]_n ( 2 ) (H₄bptc = biphenyl‐3,3′,5,5′‐tetracarboxylic acid, DMF = N,N′‐dimethylformamide, DMA = N,N′‐dimethylacetamide), were obtained under solvothermal conditions by varying the reaction solvents. Single crystal X‐ray diffraction analyses revealed that compound 1 features a 3D PtS type framework based on dinuclear [Zn₂O(COO)₂] subunits and compound 2 features a 3D lvt type framework based on paddle‐wheel shaped [Zn₂(COO)₄] subunits. Moreover, the luminescent and thermal stabilities of these two compounds were investigated.     

Strain‐Induced Isomerization in One‐Dimensional Metal–Organic Chains

The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution‐ and solid‐phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom‐up on‐surface synthesis of well‐defined nanostructures. We report an internal strain‐induced skeletal rearrangement of one‐dimensional (1D) metal–organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu‐catalyzed debromination of organic monomers to generate 1,5‐dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond‐resolved non‐contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate‐induced internal strain drives the skeletal rearrangement of MOCs via 1,3‐H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain‐induced structural rearrangement in 1D systems will enrich the toolbox for on‐surface synthesis of novel functional materials and quantum nanostructures.