Coordination behavior of chromone Schiff bases towards the [ReVO]3+ and [ReI(CO)3]+ cores

Herein, we describe the coordination behavior of chromone Schiff bases towards [Re^VO]³⁺ and [Re^I(CO)₃]⁺. The reaction between 2-(2-thiolphenyliminomethyl)-4H-chromen-4-one (Htch) and [Re(CO)₅Cl] led to fac-[Re(CO)₃(bsch)Cl] (1) (bsch = 2-benzothiazole-4H-chromen-4-one). The square pyramidal [ReO(Hns)] (2) {H₂ns=bis-[(2-phenylthiolate)iminomethyl]-methyl-1-(2-hydroxyphenyl)prop-2-en-1-one} and octahedral [ReO(OCH₃)(PPh₃)(Huch)] (3) complexes were isolated from reactions of trans-[Re^VOBr₃(PPh₃)₂] with Htch and H₃uch [(5Z)-5-((4-hydroxy-2-methoxy-2H-chromen-3-yl)methyleneamino)-6-amino-1,3-dimethylpyrimidine-2,4(1H, 3H)-dione], respectively. The chromone Schiff bases and their metal complexes were fully characterized via NMR-, IR- and UV–Vis spectroscopy, single crystal XRD analysis and conductivity measurements. In addition, DFT studies were conducted to compare selected optimized and experimental parameters of the complexes.     

One-Pot Synthesis and Methylation of 3-[2-(1H-Benzimidazol-2-yl-Sulfanyl)-Acetyl]-Chromen-2-Ones

Abstract

3-(2-Bromoacetyl)coumarins (I), when treated with 2-mercatobenzimidazole (II) in acetone containing K₂CO₃ (mild base) and tetrabutylammonium bromide (TBAB) as a phase transfer catalyst, at room temperature yielded the title compound 3-[2-(1H-benzimidazole-2-yl-sufanyl)-acetyl]-chromen-2-one (III) in a one-pot synthesis. Alternatively, III could also be prepared by treating dithiocarbonic acid O-ethyl ester, S-[2-oxo-2-(2-oxo-2H-chromen3-yl)-ethyl] ester (V), with o-phenylenediamine (VI). The methylation of the title compound III was performed with dimethyl sulfate (DMS), in acetonitrile containing TBAB and K₂CO₃ at room temperature, resulting in 3-[2-(N-methyl-benzimidazol-2-yl-sulfanyl)]-acetyl-chromen-2-ones (VII). Alternatively, methylation of III could also be performed with DMS in acetonitrile containing K₂CO₃ as base and clay as surface catalyst. All the compounds were synthesized in good yields and their structures were confirmed by spectral and analytical data.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: ¹H NMR of IIIB, VB and VIIB]     

The Reaction of 3-Formylchromone with ortho-Substituted Anilines. Preparation of a Tetraaza [14]annulene

The reactions of 3-formylchromone ( 1 ) with 1, 2-phenylenediamine, 2-amino-diphenylamine and 2-aminophenol were reinvestigated and shown to yield 1, 8-dihydro-6, 13-di (2-hydroxybenzoyl)-dibenzo [b, i]-l, 4, 8, 11-tetraazacyclotetradeca- 4, 6, 11,13-tetraene ( 7 ), 3-[2-(1-phenyl)benzimidazolyl]chromone ( 10b ) and 3-(2-hydroxyphenyl)iminomethylchromone ( 4 ), respectively at variance with earlier reports. Compound 4 reacts with ethanol to give 2-ethoxy-3-[(2-hydroxyphenyl)-aminomethylidene]chroman-4-one ( 5b ). Dehydrogenation of 7 produces 3-(2-benz-imidazolyl)chromone ( 10a ), also at variance with earlier reports. The structures have been elucidated with the aid of NMR. and mass spectra. The reaction mechanism is discussed.     

两种3D微孔Zn-MOF对水溶液中Fe3+、Cr2O72-和丙酮分子的荧光传感(英文)

通过溶剂热法合成了2种三维微孔锌金属有机框架材料,其分子式为[Zn₃(DBA)(OH)(1,10-phen)₂]_n (1)和{[Zn₂(HDBA)(4,4′-bipy)_1.5]·H₂O}_n (2)(H₅DBA=3,5-二(2′,4′-对羧基苯基)苯甲酸;1,10-phen=1,10-菲咯啉;4,4′-bipy=4,4′-联吡啶)。结构分析表明,配合物1为三核锌基金属单元的三维微孔骨架,配合物2为双核锌基的微孔结构。与2相比,配合物1在水中具有较强的发光性能,可作为检测Fe³⁺、Cr₂O₇^2-和丙酮分子的发光传感器,具有较高的选择性和灵敏度。     

Copper(II) Halide Complexes of 2-Aminopyrimidines: Crystal Structures of [(2-aminopyrimidine) n CuCl2] (n=1,2) and (2-amino-5-bromopyrimidine)2CuBr2

The reaction of CuX₂(X=Cl, Br) with 2-aminopyrimidine in aqueous solution, or 2-amino-5-bromopyrimidine in aqueous acid yields compounds of the forms [LCuCl₂] _n (1), [L₂CuCl₂] (2) and [L'₂CuBr₂] (3) [L=2-aminopyrimidine; L'=2-amino-5-bromo-pyrimidine]. The three compounds all form layered structures in which each copper ion is coordinated to two 2-aminopyrimidine molecules and two halide ions. Common structural threads involve bridging ligation [either by monomeric (1) or hydrogen bonded ligand dimers (2 and 3)], N-H···X and N-H···N hydrogen bonding and π-π stacking interactions as well as semi-coordinate Cu···X bond formation (1 and 2) or Br···Br interactions (3). Compounds 1 and 2 crystallize as two-dimensional coordination polymers with asymmetrically bihalide bridged (CuX₂) _n chains cross-linked into sheets by the 2-aminopyrimidine molecules (1) or by hydrogen bonded L₂ dimers (2). The halide bibridged chains expand their primary copper coordination spheres to give 4 + 2 coordination spheres in 1 and 2. In 3, the layer structure involves coordination of the hydrogen bonded L'₂ dimers and C-Br···Br- interactions. Crystal data: (1): monoclinic, P2₁/m, a=3.929(1), b=12.373(2), c=7.050(1)å, β=91.206(4)°, V=342.7(1)&Aringsup3;, Z=2, D _calc= 2.225Mg/m³, μ=3.878 mm^-1, R=0.0269 for [|I|≥3σ(I)]. For (2): triclinic, P-1, a=4.095(4), b=7.309(5), c=10.123(6) å, α=86.28(6), β=78.44(6), γ=74.55(8)°, V=286.1(4) ų, Z=1, D _calc=1.884 Mg/m³, μ=2.360 mm^-1, R=0.0506 for [|I|≥2σ(I)]. For (3): triclinic, P-1, a=6.074(4), b=7.673(3), c=8.887(3) å, α=108.43(3) β=100.86(5), γ=106.96(4)°, V=357.0(3) ų, Z=1, D _calc=2.657 Mg/m³, μ=12.714mm^-1, R=0.0409 for [|I|≥2σ(I)].     

Secondary metabolites from marine-derived Streptomyces antibioticus strain H74-21

A new secondary metabolite, (2S,3R)-l-threonine, N-[3-(formylamino)-2-hydroxybenzoyl]-ethyl ester (streptomyceamide C, 1), together with four known compounds 1, 4-dimethyl-3-isopropyl-2,5-piperidinedione (2), cyclo-((S)-Pro-8- hydroxy-(R)-Ile (3), cyclo-((S)-Pro-(R)-Leu (4), and seco-((S)-Pro-(R)-Val) (5), were isolated from the EtOH extract of the fermented mycelium of the marine-derived streptomycete strain H74-21, which was isolated from sea sediment in a mangrove site. The structure of the new compound was established on the basis of its spectroscopic data, including 1D and 2D NMR, HR-TOF-MS. Their antifungal activities against Candida albicans and cytotoxicities against human breast adenocarcinoma cell line MCF-7, human glioblastoma cell line SF-268 and human lung cancer cell line NCI-H460 were tested. Compounds 1 only displayed cytotoxicity against human breast adenocarcinoma cell line MCF-7 with the IC₅₀ value of 27.0 μg/mL. However, compounds 1–5 do not show antifungal activities at the test concentration of 1 mg/mL, and 2–5 have no cytotoxicities at the test concentration of 50 μg/mL.     

Synthesis and antimicrobial activity of new derivatives of pyrano[4',3':4',5']pyrido[3',2':4,5]thieno[3,2-d]pyrimidine and new heterocyclic systems

Taking into account previously obtained biological results on some polyheterocyclic compounds (containing different heteroatoms) and in particular on several 8-amino-5-isopropyl-2,2-dimethyl-10-(methylthio)-1,4-dihydro-2H-pyrano[4’’,3’’:4’,5’]pyrido[3’,2’:4,5]thieno[3,2-d]pyrimidines Ia-v we have carried out the synthesis of twentyone 8-amino-5-isobutyl-2,2-dimethyl-10-(methylthio)-1,4-dihydro-2H-pyrano[4’’,3’’:4’,5’]pyrido[3’,2’:4,5]thieno[3,2-d]pyrimidines 6. Therefore we have slightly modified the structure of the previously studied I introducing at C-5 an isobutyl group instead of the previously examined isopropyl ones in order to see if this variation (changing a little the lipophilicity) will affect the biological activity. Furthermore thieno[3,2-d]pyrimidine-8-thione 7 and their S-alkylated 8 were synthesized. Finally by alkylation of 5-isobutyl-2,2-dimethyl-10-thioxo-1,4,10,11-tetrahydro-2H-pyrano[4'',3'':4',5']pyrido[3',2':4,5]thieno[3,2-d]pyrimidin-8(9H)-one 3 with alkyl dichlorides (bifunctional reagents) we realized the cyclization of a thiazole or thiazine ring on the [b] side of the pyrimidine ring with formation of the new condensed pentaheterocyclic systems: pyrano[4'',3'':4',5']pyrido[3',2':4,5]thieno[3,2-d][1,3]thiazolo[3,2-a]pyrimidin-8-one 11 and pyrano[4''',3''':4'',5'']pyrido[3'',2'':4',5']thieno[3',2':4,5]pyrimido[2,1-b][1,3]thiazin-8-one 12. It was found that some of the synthesized compounds showed interesting antimicrobial activity (by agar diffusion method) against some gram-positive and gram-negative bacilli strains.     

Ni(II) and Cu(II) complexes of new unsymmetrical N2O2 Schiff bases derived from 3-(2-aminobenzylimino)-1-phenylbutan-1-ol: synthesis,structure, antibacterial properties,and electrochemistry

Two new N₂O₂ unsymmetrical Schiff bases, H₂L¹ = 3-[({o-[(E)-(o-hydroxyphenyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol and H₂L² = 3-[({o-[(E)-(2-hydroxy-1-naphthyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol, and their copper(II) and nickel(II) complexes, [CuL¹] (1), [CuL²] (2), [NiL¹] (3), and [NiL²] (4), have been synthesized and characterized by elemental analyses and spectroscopic methods. The crystal structures of these complexes have been determined by X-ray diffraction. The coordination geometry around Cu(II) and Ni(II) centers is described as distorted square planar in all complexes with the CuN₂O₂ coordination more distorted than the Ni ones. The electrochemical studies of these complexes indicate a good correlation between the structural distortion and the redox potentials of the metal centers. The ligand and metal complexes were also screened for their in vitro antibacterial activity.     

Synthesis,structures, and urease inhibition of nickel(II), zinc(II), and cobalt(II) complexes with similar hydroxy-rich Schiff bases

Four new nickel(II), zinc(II), and cobalt(II) complexes, [Zn(L¹)₂]?·?H₂O (1), [Ni(L¹)₂]?·?H₂O (2), [Ni(L²)₂] (3), and [Co(L³)₂]?·?H₂O (4), derived from hydroxy-rich Schiff bases 2-{[1-(5-chloro-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL¹), 2-{[1-(2-hydroxy-3-methoxyphenyl)methylidene]amino}-2-ethylpropane-1,3-diol (HL²), and 2-{[1-(5-bromo-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL³) have been synthesized and characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray determination. Each metal in the complexes is six-coordinate in a distorted octahedral coordination. The Schiff bases coordinate to the metal atoms through the imino N, phenolate O, and one hydroxyl O. In the crystal structures of HL¹ and the complexes, molecules are linked through intermolecular O–H···O hydrogen bonds, forming 1-D chains. The urease inhibitory activities of the compounds were evaluated and molecular docking study of the compounds with the Helicobacter pylori urease was performed.     

Synthesis,structure, DNA-binding,and cytotoxic activities of N-(5-chloro-2-hydroxyphenyl)-N′-[3-(2-hydroxyethylamino)propyl]oxamide and its dicopper(II) complex

A dissymmetrical N,N′-bis(substituted)oxamide, N-(5-chloro-2-hydroxyphenyl)-N′[3-(2-hydroxyethylamino)propyl]oxamide (H₃oxpep), and its dicopper(II) complex, [Cu₂(oxpep)(phen)]ClO₄ (1) (phen?=?1,10-phenanthroline), were synthesized. The crystal structure of 1 was determined by single-crystal X-ray diffraction. In 1, Cu1 and Cu2 are bridged by cis-oxpep^3? with Cu?···?Cu separation of 5.2007(6)?Å. Cu1 is in a distorted square-pyramidal environment, while Cu2 has a square-planar coordination geometry. The 3-D supramolecular structure of 1 is formed through π–π stackings and hydrogen bonds. The DNA-binding properties and cytotoxic activities of the two compounds were investigated. The results suggest that the two compounds can interact with HS-DNA by intercalation with binding affinities following the order 1?>?H₃oxpep, which is consistent with their anticancer activities.     

Six new 2-(2-phenylethyl)chromones from Agarwood

Six new chromones, 6-methoxy-2-[2-(3-methoxy-4-hydroxyphenyl)ethyllchromone (2), 6,8-dihydroxy-2-(2-phenylethyl)chromone (3), 6-hydroxy-2-[2-(4-hydroxyphenyl)ethyl]chromone (4), 6-hydroxy-2-[2-(2-hydroxyphenyl)ethyl]chromone (5), 7-hydroxy-2-(2-phenylethyl)chromone (6), and 6-hydroxy-7-methoxy-2-(2-phenylethyl)chromone (7) were isolated from the ether extract of agarwood in addition to a known compound, 2-(2-phenylethyl)chromone or flidersiachromone (1). Their structures were determined by spectroscopic methods including UV, IR, and NMR spectral data and comparisons with the calculated values using the hydroxyl and methoxyl substituent increments of the chromone ring.     

Metal ion-assisted assembly of one-dimensional polyrotaxanes incorporating cucurbit[6]uril

Three cucurbit[6]uril (CB[6])-based polyrotaxanes [Cu(H₂ C6N4)(CB[6])]Cl₄·12H₂O (1), [Co(H₂ C6N4)(CB[6])]Cl₄·14H₂O (2) and [Ag(C6N4)(CB[6])]NO₃·7H₂O (3) are prepared using N,N′-bis(4-pyridylmethyl)-1,6-hexanediamine (C6N4) threading into CB[6]'s and metal ions' assistance. Single-crystal X-ray diffraction analyses reveal that polyrotaxanes 1, 2 and 3 all have 1D chain structure where 1 and 2 are linear and 3 has two shapes, linear and sawtooth, respectively. The effects of guest molecules, metal and counter ions as well as intermolecular weak interactions on the architectures of polyrotaxanes are discussed.     

Supramolecular complexes constructed with carboxylate Cu(II) and 2-(2-pyridyl)-benzimidazole via hydrogen bonding

Four copper(II) supramolecular complexes, {[Cu(Hpb)(mal)]·H₂O} _n (1), (Hpb?=?2-(2-pyridyl)-benzimidazole, mal?=?maleate), [Cu₄(pb)₄(cro)₄(MeOH)₂]·2MeOH (2) (cro?=?crotonate), [Cu₂(pb)(Hpb)(mac)₃(MeOH)] (3) (mac?=?α-methacrylate) and [Cu(Hpb)(acr)₂(H₂O)] (4) (acr?=?acrylate), based on carboxylate copper(II)-aromatic ligand systems which are assembled by combination of metal coordination, hydrogen-bond and π–π interactions, have been rationally designed and synthesized. Complex 1 forms a 3D supramolecular network with open channels by extending 2D undulating sheets constructed from 1D helical chains. Complex 2 generates a 2D grid-like sheet via unusual finite-chain tetranuclear molecules, with four copper atoms arranged in a line; the unit does not extend further due to the capping effect of the terminal methanol. Complexes 3 and 4 present a 1D sinusoidal structure and a 3D columnar network with 1D ladder-shaped double chains, respectively. Interestingly, coligand Hpb, deprotonated or/and neutral in different supramolecular complexes, provides hydrogen bonding and π–π stacking interactions. In complexes 2, 3 and 4, carboxylate anions show various bridging modes, which are reflected in their magnetic properties. Weak ferromagnetic coupling (syn-anti µ-OCO) exists in 1, antiferromagnetic (syn-syn µ-OCO) and weak ferromagnetic coupling (µ-O of the??COO group) in 2 and antiferromagnetic coupling (syn-syn µ-OCO) in 3.     

Hepatoprotective phenylethanoid glycosides from Cirsium setosum

Two new phenylethanoid glycosides, namely β-D-glucopyranoside, 1″-O-(7S)-7-(3-methoxyl-4-hydroxyphenyl)-7-methoxyethyl-3″-α-L-rhamnopyranosyl-4″-[(8E)-7-(3-methoxyl-4-hydroxyphenyl)-8-propenoate] (1) and β-D-glucopyranoside, 1″-O-(7S)-7-(3-methoxyl-4-hydroxyphenyl)-7-methoxyethyl-3″-α-L-rhamnopyranosyl-4″-[(8E)-7-(4-hydroxyphenyl)-8-propenoate] (2), together with six phenylethanoid glycosides were isolated from Cirsium setosum. Their structures were elucidated by their spectroscopic data and references. Compounds 2, 4, 5, 7 and 8 (10 μM) exhibited moderate hepatoprotective activities. Compounds (3–8) were obtained from this plant for the first time.     

Preparation and structural characterization of oxovanadium(V) complexes with Schiff bases and their inhibition studies on Helicobacter pylori urease

A series of structurally similar dinuclear oxovanadium(V) complexes, [VO₂L]₂ (L?=?L¹?=?2-[(2-methylaminoethylimino)methyl]phenolate (1); L?=?L²?=?2-[(2-ethylaminoethylimino)methyl]phenolate (2); L?=?L³?=?2-[(2-isopropylaminoethylimino)methyl]phenolate (3)), has been synthesized and characterized by physico-chemical methods and single-crystal X-ray diffraction. The V in each complex is octahedral, with three donors of L and one oxo defining the equatorial plane, and with two oxos occupying the axial positions. The complexes were tested for their urease inhibitory activities. The inhibition rate (%) of 1, 2, and 3 at 100?µmol?L^?1 on urease are 67?±?1, 53.5?±?0.9, and 44?±?1. The relationship between structures of the complexes and the urease inhibitory activities indicates that shorter terminal groups of the complexes have stronger activities against urease. Molecular docking study of the complexes with the Helicobacter pylori urease was performed.     

Tetranuclear cobalt(II) complex and trinuclear copper(II) complex with the ligand 2-hydroxy-3-[(2-sulfoethylimino)-methyl]-benzoic acid: synthesis,structure and properties

A cobalt(II) compound, [Co₄(L)₂(OH)₂(phen)₂(H₂O)₄] · 6H₂O (1), and a copper(II) compound, [Cu₂(L)₂(H₂O)₂][Cu(H₂O)₆] · 6H₂O (2) [where H₃L is 2-hydroxy-3-[(2-sulfoethylimino)-methyl]-benzoic acid and phen is O-phenanthroline], were prepared and characterized. The tetranuclear cobalt complex 1, C₄₄H₆₂N₆O₂₈S₂Co₄, crystallizes in the monoclinic space group P2₁/c, with a = 11.847(10) Å, b = 19.061(15) Å, c = 12.635(10) Å, β = 105.483(9)°, and Z = 2; R ₁ for 4821 observed reflections [I > 2σ(I)] was 0.0679. Complex 1 is a centrosymmetric tetranuclear cobalt complex with all cobalts having distorted octahedral geometry. The molecule can be viewed as two planar [Co₂(OH)(L)(Phen)H₂O] units tied together by two terminal water molecules. The framework of 1 has the appearance of two connected face-sharing cubes, each with one vertex missing. The trinuclear copper complex 2, C₂₀H₄₄Cu₃N₂O₂₆S₂, crystallizes in the triclinic space group P1, with a = 7.524(1) Å, b = 7.902(2) Å, c = 16.885(4) Å, α = 88.993(6)°, β = 80.725(7)°, γ = 66.725(4)° and Z = 1; R ₁ for 4298 observed reflections [I > 2σ (I)] was 0.0360. Complex 2 is an ionic compound, in which the three Cu(II) centers have two coordination modes. The molecule has a centrosymmetric dinuclear copper coordinated anion and a hexa-aqua-copper cation. The sulfonic acid group has less coordination ability than carboxylate oxygen.     

Substrate-induced adjustment of “slipped” π–π stacking: en route to obtain 1D sandwich chain and higher order self-assembly supramolecular structures in solid state

‘Slipped’ π?π stacking between flexible macrocycle 1⁴⁺ (cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](1,4-dimethylene benzene)) and neutral small molecules induce one-dimensional (1D) ‘sandwich’ chain self-assembly. Unlike most of the reported π?π stacking system, the 1D “sandwich” chain expands with the direction parallel to stacking π surfaces on 1⁴⁺ and that on molecule 2, 3, 4 or 5 (2 = p-xylene, 3 = benzene-1,4-diamine, 4 = 4,4′-bipyridine, 5 = [1,1′-biphenyl]-4,4′-diol). Moreover, the π?π stacking modes of 1D self-assembly are seriously small molecule adduct dependent. Combined with the other weak interactions (e.g. intermolecular hydrogen bonding), the new substrate design and control strategy can expand the 1D ‘sandwich’ chain (e.g. [1⁴⁺·4]_n) into higher order structure (e.g. two-dimensional (2D) network [1⁴⁺·4·6]_n, 6 = hydroquinone) even in large scale (~280 mg). This 2D network structure, which keeps stable under 423 K, shows highly selective gas absorption of CO₂ over N₂.     

Synthesis,characterization, and antimicrobial activities of a dinuclear copper(II) complex with bis(2-[(2-hydroxy-ethylimino)-methyl]-4,6-diiodo-phenol)

A dinuclear copper(II) complex with a newly synthesized tridentate Schiff-base ligand 2-[(2-hydroxy-ethylimino)-methyl]-4,6-diiodo-phenol (HL), of formula [Cu₂L₂Cl₂?·?C₄H₈O] (1), was prepared. Both the ligand and the complex were characterized by X-ray crystallography, confirming that the Schiff base is tridentate and its dinuclear copper(II) complex is five-coordinate from one nitrogen and two oxygens from L and two chlorides. The complex was assayed for antibacterial (Bacillus subtilis, Staphylococcus aureus, Streptococcus faecalis, Pseudomonas aeruginosa, Escherichia coli, and Enterobacter cloacae) activities by the MTT method. Complex 1 exhibited better antimicrobial activity than the ligand.     

Azocalixarenes. 6: Synthesis, complexation, extraction and thermal behaviour of four new azocalix[4]arenes

Four new azocalix[4]arenes {5,11,17,23-tetrakis[(2-hydroxy-5-tert-butylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (1), 5,11,17,23-tetrakis[(2-hydroxy-5-nitro phenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (2), 5,11,17,23-tetrakis[(2-amino-5-carboxylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (3) and 5,11,17,23-tetrakis[(1-amino-2-hydroxy-4-sulfonicacidnapthylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (4)} have been synthesized from p-tert-butylphenol, p-nitrophenol, p-aminobenzoic acid and 1-amino-2-hydroxy-4-sulphonic acid by diazo coupling reaction with p-aminocalix[4]arene. The resulting ligands (1–4) were treated with three transition metal salts (e.g., CuCl₂·2H₂O, NiCl₂·6H₂O or CoCl₂·6H₂O). Cu(II), Ni(II) and Co(II) complexes of the azocalix[4]arene derivatives were obtained and characterized by UV-vis, IR, ¹H-NMR spectroscopic techniques and elemental analysis. All the complexes have a metal:ligand ratio of 2:1. The Cu(II) and Ni(II) complexes of azocalix[4]arenes are square-planar, while the Co(II) complexes of azocalix[4]arenes are octahedral with water molecules as axial ligands. The solvent extraction of various transition metal cations from the aqueous phase to the organic phase was carried out by using azocalix[4]arenes (1–4). It was found that, azocalix[4]arenes 1, 2 and 3 examined selectivity for transition metal cations such as Ag⁺, Hg⁺ and Hg²⁺. In addition, the thermal stability of metal:azocalix[4]arene complexes were also reported. Dedicated to Prof. Dr. Mustafa Yılmaz on the occasion of his 50th birthday     

4-(2-(4-咪唑)苯乙烯基)吡啶和三种芳香二羧酸的Cd(Ⅱ)配位聚合物的合成、结构及荧光性质

以4-(2-(4-咪唑)苯乙烯基)吡啶(ISPE)为配体,分别与间苯二甲酸(1,3-H_2BDC)、4,4′-联苯二甲酸(4,4′-H_2BPDC)和4,4′-二苯乙烯二甲酸(4,4′-H_2STDC)及过渡金属盐Cd(NO3)2·4H_2O通过溶剂热自组装形成了3种配位聚合物晶体{[Cd_2(ISPE)_2(1,3-BDC)_2]·DMF}_n(1)、[Cd(ISPE)(4,4′-BPDC)]_n(2)和[Cd(ISPE)_2(4,4′-STDC)(H_2O)_2]_n(3)。并用单晶X射线衍射、PXRD、红外光谱、元素分析、热重等对其进行了表征。单晶解析结果表明:配位聚合物1是二维层状网格结构,配位聚合物2是一个六重穿插的类金刚烷三维网格结构,配位聚合物3是由一维网格结构通过氢键和分子间作用力堆积形成的三维网格结构。另外还研究了它们的室温固态荧光性能。