Synthesis and crystal structure of a new zinc diphosphonate

A new zinc diphosphonate [NH₃CH(CH₃)CH₂NH₃]₂Zn₂(edbbp)₂(HNO₃)₂·4H₂O [eddbp?= O₃PCH(Ph)NH(CH₂)₂NHCH(Ph)PO₃] was hydrothermally synthesized with Zn(NO₃)₂·6H₂O, ethane-1,2-diamino-N,N′-bis(benzylphosphonic acid) (H₄edbbp) and 1,2-propyldiamine. It consists of a centro-symmetric dimeric unit [Zn₂(edbbp)₂], in which each zinc ion adopts a distorted square-pyramidal coordination geometry. Hydrogen bonds formed between phosphonate groups and protonated 1,2-propyldiamine molecules link the dimeric units into one-dimensional chains. The doubly protonated 1,2-propyldiamine molecules serve not only as charge compensating counter ions, but also as bridging groups. Hydrogen-bonding interactions among the phosphonate oxygen atoms, water molecules, nitric acid molecules and protonated 1,2-propyldiamine result in the formation of a three-dimensional supramolecular network.     

Synthesis,crystal structure and photoluminescence of a three‐dimensional zinc coordination compound with NBO‐type topology

The assembly of metal–organic frameworks (MOFs) with metal ions and organic ligands is currently attracting considerable attention in crystal engineering and materials science due to their intriguing architectures and potential applications. A new three‐dimensional MOF, namely poly[[diaqua(μ₈‐para‐terphenyl‐3,3′,5,5′‐tetracarboxylato)dizinc(II)] dimethylformamide disolvate monohydrate], {[Zn₂(C₂₂H₁₀O₈)(H₂O)₂]·2C₃H₇NO·H₂O}_n, was synthesized by the self‐assembly of Zn(NO₃)₂·6H₂O and para‐terphenyl‐3,3′,5,5′‐tetracarboxylic acid (H₄TPTC) under solvothermal conditions. The compound was structurally characterized by FT–IR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction analysis. Each Zn^II ion is located in a square‐pyramidal geometry and is coordinated by four carboxylate O atoms from four different TPTC^4? ligands. Pairs of adjacent equivalent Zn^II ions are bridged by four carboxylate groups, forming [Zn₂(O₂CR)₄] (R = terphenyl) paddle‐wheel units. One aqua ligand binds to each Zn^II centre along the paddle‐wheel axis. Each [Zn₂(O₂CR)₄] paddle wheel is further linked to four terphenyl connectors to give a three‐dimensional framework with NBO‐type topology. The thermal stability and solid‐state photoluminescence properties of the title compound have also been investigated.     

Synthesis, crystal structure and photoluminescence of 2,6-dimethylanthracene and its pseudo-triptycene derivatives

A simple one-step synthesis of 2,6-dimethylanthracene, 1, in high yield is reported utilizing the easily accessible benzyl alcohol as the starting material. Based on 2,6-dimethylanthracene, two pseudo-triptycene compounds, cis-2,6-dimethyl-9,10-dihydroanthracene-9,10-endo-α,β-succinic anhydride, 2, and cis-2,6-dimethyl-9,10-dihydroanthracene-9,10-endo-α,β-succinyl amine, 3, are firstly synthesized in high yield and they are characterized by single crystal X-ray diffraction. Compound 2 crystallizes in triclinic space group and compound 3 crystallizes in monoclinic P2₁/c space group. Both compound 2 and 3 exhibit cis-configurations and endo-conformations. Compound 1 exhibits very intense photoluminescence property due to the delocalized electron in the whole molecule, whereas fluorescence quench happens to some extents due to the destruction of the conjugated structure in compound 2.     

Hydrothermal synthesis,crystal structure and photoluminescence of two homochiral zinc(II) coordination polymers

Metal–organic frameworks (MOFs) have potentially useful applications and an intriguing variety of architectures and topologies. Two homochiral coordination polymers have been synthesized by the hydrothermal method, namely poly[(μ‐N‐benzyl‐L‐phenylalaninato‐κ⁴O,O′:O,N)(μ‐formato‐κ²O:O′)zinc(II)], [Zn(C₁₆H₁₆NO₂)(HCOO)]_n, (1), and poly[(μ‐N‐benzyl‐L‐leucinato‐κ⁴O,O′:O,N)(μ‐formato‐κ²O:O′)zinc(II)], [Zn(C₁₃H₁₈NO₂)(HCOO)]_n, (2), and studied by single‐crystal X‐ray diffraction, elemental analyses, IR spectroscopy and fluorescence spectroscopy. Compounds (1) and (2) each have a two‐dimensional layer structure, with the benzyl or isobutyl groups of the ligands directed towards the interlayer interface. Photoluminescence investigations show that both (1) and (2) display a strong emission in the blue region.     

Synthesis, Structure and Photoluminescence of Two Zinc Carboxyl－ate Polymers with Different Coordination Architectures

The hydrothermal reaction of ZnO with benzene‐1,4‐dicarboxylic add gave Zn·BDC·2H₂O (1) and Zn‐BDC·H₂O (2) (BDC = benzene‐1, 4‐dicarboxylate), respectively. Polymer 1 (C₄H₄O₃ZH_0.5) shows a one‐dimensional zigzag chain structure built up from the alternate connection of tetrahedral ZnO₄ and BDC units. Polymer 2 (C₄H₃O_2.5Zn_0.5) possesses a three‐dimensional framework containing infinite zigzag Zn·Zn·Zn pseudochains generated by five‐coordinate zinc centers and a rectangular channel system including three groups of different straight channels along the [001], [010] and [60–1] directions. The two metal‐organic polymeric compounds exhibit strong photoluminescent emission bands at 402 nm (λ_ex = 260 nm) (for 1) and at 344 nm and 385 nm (λ_ex = 279 nm) (for 2) in the solid state at room temperature.     

Synthesis,crystal structure,photoluminescence properties of organic-inorganic hybrid materials based on ethylenediamine bromide

In this work, a new orthorhombic organic-inorganic hybrid single crystal (C₂H₁₀N₂)₂MnBr₄.2Br with-Zero-dimensional structure was synthesized by slow evaporation method at 75 °C. The crystal structure and intermolecular interactions were performed by single crystal X-ray diffraction and Hirshfeld surface. Optical properties of (C₂H₁₀N₂)₂MnBr₄.2Br were systematically studied by Raman, infrared spectrum, UV–vis, photoexcitation spectra, and photoluminescence spectra. The optical band gap (E_g = 2.61 eV) were calculated from the absorption spectra of (C₂H₁₀N₂)₂MnBr₄.2Br. This hybrid materials also had shown good thermal stability (decomposition temperature: 288–660 °C). Finally, photoluminescence measurements showed a strong excitation line at 362 nm and a strong fluorescence at 537 nm which makes it a promising material in luminescence field.     

3D zinc(II) coordination polymers built up by triazole and benzene-polycarboxylate anions: Synthesis,crystal structure,thermal and photoluminescence characterization

Two coordination polymers of the formula [Zn₅(tmaH)₄(trz)₂(H₂O)₄] (1) and [Zn₃(bta)(trz)₂(H₂O)₄]·2H₂O (2) [tmaH₃ = benzene-1,3,5-tricarboxylic acid/trimesic acid, trzH = 1,2,4-triazole, btaH₄ = benzene-1,2,4,5-tetracarboxylic acid] have been synthesized and structurally characterized by X-ray single crystal diffraction analysis. Both complexes are 3D coordination polymers containing [Zn₄(trz)₂] units connected by benzene-carboxylate anions. In particular, an undulated layer containing 6- and 18-membered rings is outlined in the network of 1. Hydrogen bonds, involving the coordinated and lattice water molecules with carboxylate oxygen atoms, contribute to the stabilization of the networks. Their thermal stability was investigated by thermogravimetric analysis. The fluorescence spectrum of 1 features two peaks at 419 and 323 nm, originating from a π–π∗ intraligand transition and LMCT, respectively. For 2 a broad band at 410 nm is assigned solely as a π–π∗ intraligand transition.     

Synthesis,crystal structure,and electroluminescent properties of zinc and cadmium tetradentate azomethine complexes

Chemical and electrochemical syntheses of zinc(II) and cadmium(II) complexes based on tetradentate Schiff bases (H₂L¹ and H₂L²) resulting from condensation of 2-tosylaminobenzaldehyde with 3,6-dioxa-1,8-octanediamine or 4,9-dioxa-1,12-dodecanediamine were performed. The structure, composition, and properties of the complexes were studied by elemental analysis, IR, ¹H NMR, and UV spectroscopy, X-ray absorption spectroscopy, and X-ray diffraction. The zinc(II) and cadmium(II) complexes luminesce in a DMF solution in the blue spectral region (λ_PL = 425–433 nm), the photoluminescence quantum yield φ being 0.25–0.30. Multilayer zinc(II)- and cadmium(II)-based electroluminescent structures with green-blue emission of the exciplex nature were fabricated.     

A 3D porous zinc MOF constructed from a flexible tripodal ligand: Synthesis, structure, and photoluminescence property

A new metal-organic framework, [Zn₅(trencba)₂(OH)₂Cl₂·4H₂O] (1) [H₃trencba=N,N,N′,N′,N′′,N′′-tris[(4-carboxylate-2-yl)methyl]-tris(2-aminoethyl)amine], constructed from a flexible tripodal ligand based on C₃ symmetric tris(2-aminoethyl)amine, has been synthesized hydrothermally and characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction analysis. Compound 1 contains an unprecedented linear penta-nuclear zinc cluster fragment. Each ligand links four penta-nuclear fragments, and every fragment links eight ligands to generate a three-dimensional non-interpenetrated porous framework. The uncoordinated water molecules were observed trapped in the void pores. Compound 1 represents the first example of (6,8)-connected 3D bi-nodal framework based on a single kind of organic ligand. The photoluminescence measurements showed that complex 1 exhibits relatively stronger blue emissions at room temperature than that of the ligand.     

Synthesis,crystal structure,and DNA binding of a new oxalato-bridged binuclear zinc(II) complex

A new binuclear zinc(II) complex bridged by μ-oxalate, and end-capped with 2,2′-bipyridine (bpy), [Zn₂(ox)(bpy)₄](ClO₄)₂ · H₂O, has been synthesized and characterized by elemental analyses, molar conductance, IR, and electronic spectra and single-crystal X-ray diffraction. The single-crystal X-ray analysis reveals that the [Zn₂(ox)(bpy)₄]²⁺ cation has two zinc(II) centers bridged by a planar bis(bidentate) oxalate group with Zn···Zn distance of 5.482(3) Å; each zinc(II) is in a distorted octahedral environment. The crystal structure is stabilized by non-classical C–H···O hydrogen bonds and π–π stacking interactions to form a 3-D supramolecular structure. The interaction of the complex with calf-thymus DNA (CT-DNA) was explored by using electronic and fluorescence spectra and viscosity measurements. The results reveal that the complex intercalates with CT-DNA with intrinsic binding constant of 4.1 × 10⁴ M^?1.     

Synthesis,crystal structure,and photoluminescence of a new Zn(II) molecular box compound derived from a two-armed bis-terdendate ligand

The dinuclear compound Zn₂(HL²)₂(ClO₄)₂(C₂H₅OH)_0.5(H₂O)₂ (1) based on di(2-acetylpyridyl)-6,6′-dicarboxylic acid hydrazone-2,2′-bipyridine (H₂L²) has been obtained via self-assembly. X-ray crystallography indicated the formation of a molecular box rather than a helicate. The photoluminescence properties of 1 in the solid state have an emission at ca 500 nm with excitation at 400 nm at room temperature.     

Preparation, crystal structure and photoluminescence of garnet-type calcium tin titanium aluminates

Colorless and transparent single crystals of Ca₃Sn_2.2Ti_0.8Al₂O₁₂, which emit blue-white light under ultraviolet light, were prepared by heating a mixture of oxides and calcium carbonate with a calcium and aluminum-rich composition at 1500 °C. Single crystal X-ray diffraction revealed that the crystal structure is the garnet-type with a cubic cell parameter (a=12.5309(3) Å) and the space group, Ia 3¯d (R1=0.0277, wR2=0.0663, and S=1.367 for all data). The structural formula is presented as Ca₃[Sn_0.96Ti_0.04]_octa[Al_0.67Ti_0.24Sn_0.09]_tetraO₁₂. Polycrystalline solid solutions of Ca₃Sn_3−xTi_xAl₂O₁₂ were prepared by solid state reaction in air at 1370 °C with nominal titanium contents from x=0.6 to 1.4. The refined unit cell parameter decreased with increasing x. A broad blue-white emission with a peak wavelength of 465 nm was observed for the solid solutions at room temperature.     

Synthesis,structure, and photoluminescence of a zinc(II) coordination polymer with 4-(tetrazol-5-yl)benzoate

A new coordination polymer with interesting supramolecular architecture, [Zn(4-tzbz)] _n (1) (4-tzbz = 4-(tetrazol-5-yl)benzoate), has been synthesized and characterized structurally. In this compound, the zinc(II) ions are connected by the tetrazole ring in the μ₂-1,4 bridging mode and the carboxylate group in the μ₂-1,3 syn-anti bridging mode to generate 2D (4,4) sheets, and the adjacent sheets are linked further by the benzene rings to give the 3D metal–organic framework with a 3,4-connected (8³)(8⁴12²) topology. This compound in the solid state exhibits photoluminescence assignable to intraligand transitions, and, in particular, the emission at 400 nm is significantly intensified due to the coordination of the ligand to Zn.     

Synthesis,crystal structure,and properties of cobalt,zinc, and manganese coordination polymers based on fluconazole

Three complexes based on fluconazole, namely, {[Co₂(HFlu)(dpa)₂(H₂O)₂]·H₂O}_n (1), {[Zn(HFlu)(IPA)]·H₂O}_n (2), and {[Mn(HFlu)₂(IPA)(H₂O)]·H₂O}_n (3) (HFlu?=?fluconazole, 2-(2,4-difluoro-phenyl)-1,3-bis(1,2,4-triazol-1-yl)-propan-2-ol; H₂dpa?=?diphenic acid; H₂IPA?=?isophthalic acid) have been synthesized. Single-crystal X-ray analysis revealed that 1 is a 2-D-network framework containing a trinuclear Co(II) unit, 2 is a 3-D framework, and 3 is 1-D double chain structure with a Mn₂ metallocyclic core. The complexes have also been characterized by elemental analyses, IR, UV/vis and fluorescence spectroscopy, and thermal gravimetry. The phase purity of these polymers has been confirmed via powder X-ray diffraction.     

Synthesis,crystal structure,thermal stability,and photoluminescence of a 3-D silver(I) network with twofold interpenetrated dia-f topology

A silver(I) coordination polymer with mixed 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (bpz) and maleic acid, [Ag₂(bpz)₃(fum)]_n (1, H₂fum = fumaric acid), was synthesized under hydrothermal condition by in situ isomerization of maleic acid to fumaric acid and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, TGA, and single-crystal X-ray diffraction. The maleic acid in situ isomerizes to fumaric acid and participates in the formation of 1. Topologically, the structure of 1 features a rare 3-connected twofold interpenetrated dia-f net with a point symbol of {4.14²}. Compound 1 exhibits photoluminescence in the solid state with an emission maximum at 470 nm upon excitation at 365 nm at room temperature, which is attributed to intraligand or/and interligand π → π* transition.     

Synthesis and crystal structure of two new discrete, neutral complexes of manganese and zinc using a rigid organic clip

Two discrete neutral dimanganese(II) and tetrazinc(II) complexes were synthesized from a rigid organic clip and the corresponding metal acetates. The compounds were characterized by elemental analysis and single crystal X-ray diffraction study. The manganese species is a dinuclear discrete product with two disordered acetates bridging two manganese centers, while the zinc one consists of two octahedral and two tetrahedral Zn(II) centers with both bridging acetates and triply micro(3)-hydroxides. Variable temperature magnetic measurement reveals the existence of weak antiferromagnetic interaction (J = -1.6 cm(-)(1); H = -2JS(1).S(2)) within the manganese complex.     

Preparation,catalytical activity and crystal structure of a heptanuclear zinc acetate cluster

Reaction of [Zn₄(µ₄-O)(O₂CCH₃)₆] with one equivalent of 4-tertiary-butylpyridine leads to a nearly quantitative formation of the heptanuclear cluster [Zn₇O₂(O₂CCH₃)₁₀(^tbupy)₂] (1). Here, we present the crystal structure of 1 and first results of the examination of its catalytic activity in transesterification reactions and polymerization of lactide compared to the activity of [Zn₄(µ₄-O)(O₂CCH₃)₆] in the presence of 4-tertiary-butylpyridine.     

Synthesis and crystal structure of Isotrithionedithiolato-bis(phenanthroline)zinc(II)

The synthesis of a mixed-ligand complex 1,3-dithiole-2-thione-4,5-dithiolato-bis(1,10-phenanthroline)zinc(II), [Zn(Dmit)(Phen)₂], is described. The crystals are monoclinic, space group P2₁/n, a = 11.868(2) Å, b = 13.122(3) Å, c = 17.010(3) Å, β = 102.01(3)°, Z = 4. The coordination polyhedron of the Zn(II) atom is an octahedron formed by two sulfur atoms of the Dmit ligand and four nitrogen atoms of the two Phen ligands. The complex is studied by IR and UV spectroscopy.