Sensing and photocatalytic properties of nanosized Cu(I)CN organotin supramolecular coordination polymer based on pyrazine

Orange prismatic crystals of the supramolecular coordination polymer (SCP) _∞³[Cu(CN)₂(Me₃Sn)(Pyz)], SCP 1 , were synthesized using a self‐assembly method under ambient conditions. Nanosized 1 was obtained using the same molar ratio in water by ultrasonic irradiation. SCP 1 was characterized using single‐crystal X‐ray diffraction, elemental analysis, thermal analysis and Fourier transform infrared spectroscopy. SCP 1 and its nanosized 1 particles were also examined using powder X‐ay diffraction and scanning electron microscopy. The luminescence emission of SCP 1 was studied as well as its use as a sensor for the detection of common organic solvents and metal ions. Also, the catalytic activities of nanosized 1 towards various organic dyes were investigated under ambient conditions, UV irradiation and ultrasonic irradiation. Nanosized 1 as a heterogeneous nanoparticle catalyst exhibits high catalytic activity for the degradation of eosin‐Y and acid blue dyes. The mechanism of degradation investigated using various scavenger techniques is proposed and discussed. The catalytic oxidation process is mainly caused by ?OH radicals.     

Ultrasound-assisted nanoscaled supramolecular coordination polymer as an efficient recyclable catalyst for photocatalytic degradation of dye pollutants

An ultrasound-assisted nanoscaled supramolecular coordination polymer (nanosized 1′ ) has been synthesized using a self-assembly reaction of K₃[Cu (CN)₄] and hexamethylenetetramine in the presence of Me₃SnCl under ambient conditions. Nanosized 1′ was examined using elemental analysis, Fourier transform–infrared, transmission electron microscopy, scanning electron microscopy and X-ray powder diffractions. It was structurally compared with the single crystal supramolecular coordination polymer ^∞₃[Cu₆(CN)₇(C₆H₁₂N₄)₂(OH₃)]; SCP 1. The photocatalytic activities of nanosized 1′ and SCP 1 toward different hazardous organic dyes were determined under ambient, UV-light irradiation and ultrasonic conditions. SCP 1 and nanosized 1′ as heterogeneous nanoparticles catalysts exhibited high catalytic activity for degradation of Congo Red, Methyl Violet 2B and Methylene Blue dyes. The effects of operational parameters on catalytic degradation process, identification of the degradation products and recycling of the catalyst were also investigated. SCP 1 and nanosized 1′ are recyclable heterogeneous catalysts and can be reused with efficient activities. The mechanism of degradation using different scavenger techniques iss proposed and discussed. The catalytic oxidation process is mainly caused by ^•OH radicals.     

Three‐dimensional organotin–hexacyanoferrate polymers as effective oxidizing reagents towards phenols

Three‐dimensional organotin–hexacyanoferrate polymers of the type _∞³[(R₃Sn)₃Fe^III(CN)₆] where R = Me (I), n‐butyl (II) and phenyl (III), represent members of the family of supramolecular coordination polymers (SCPs) which have zeolitic‐like structure containing micropores. The structures of I–III contain wide channels capable of encapsulating resorcinol, which undergoes in situ oxidation to 1,3,4‐trihydroxy benzene (THB) or p‐nitrophenol (PNP), which converts to 1,4‐benzoquinone (BQ) and 2‐hydroxybenzoquinone (2‐HBQ). The oxidation products were investigated by spectroscopic methods and by HPLC. The SCP III was found to be a more effective oxidizing reagent than I and II due to the presence of terminal Sn‐OH₂ groups hydrogen bonded to one‐sixth of the terminal CN groups, causing more wide expandable channels. In addition, mechanisms of the oxidation processes of resorcinol and PNP have been proposed. Copyright © 2010 John Wiley & Sons, Ltd.     

In vitro and in vivo antitumor activity of novel 3D-organotin supramolecular coordination polymers based on CuCN and pyridine bases

Two novel organotin supramolecular coordination polymers (SCP), namely, ³_∞[Me₃SnCu(CN)₂·(EN)₂], 1 and ³_∞[Ph₃SnCu(CN)₂·(3-mpy)₂], 2 are obtained by the reactions of K₃[Cu(CN)₄], ethyl nicotinate (EN) or 3-methylpyridine (3-mpy) and Me₃SnCl or Ph₃SnCl in H₂O/acetonitrile solution at room temperature. 2D-layers are constructed via H-bonds between the parallel 1D-puckered chains which contain nanometer-sized [-CN(R₃Sn)NC-] spacers connecting the tetrahedral (T-4) copper sites. The network structures of 1 and 2 consist of infinite layers connected by interlayer H-bonds forming 3D-framworks. 2 is the first compound in this family containing the Ph₃Sn cation. The electronic absorption spectra of 1 and 2 reveal a broad band at 320 nm due to CT transition while the emission spectra exhibit high energy bands at 400-460 nm due to metal-centered (MC) transitions and low energy bands at 485-530 nm corresponding to MLCT. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay was used to determine the in vitro antitumor effects of the SCP 1 and 2 on human breast cancer cell line, ZR-75-1. Cell cycle analysis revealed that the SCP 1 and 2 induced apoptosis in ZR-75-1 breast cancer cell line through activating caspase-3. Moreover, in vivo model, the compound SCP 2 suppressed tumor growth developed mammary carcinoma by 52.3%. Taken together, our novel compounds selectivity exhibit specific in vivo and in vitro antitumor effects.     

Antenna behavior of donor–acceptor dye‐loaded novel supramolecular framework hosts

New guest dye cations within the channel cavities of supramolecular hosts are studied. The guest organic dyes are intercalated in the supramolecular hosts by a coprecipitation reaction to give new dye‐sensitizer coordination polymers. The absorption spectra for the dye molecules within the supramolecular hosts show intense bands in the region from 500 to 700 nm due to the presence of the dyes within the parallel channels in the monomeric forms. The properties of the resulting colored polymers were investigated by IR, UV–vis, fluorescence spectra and X‐ray powder diffraction, indicating the excitation energy transfer from neutral red or pyronine as donors to methylene blue or thionine as acceptors within a supramolecular system filled with a mixture of both dyes. The wide‐ranging tenability of these highly organized materials offers fascinating new possibilities for exploring excitation energy transfer phenomena, and challenges for developing new photonic devices. Copyright © 2005 John Wiley & Sons, Ltd.     

<Emphasis Type="Italic">In situ</Emphasis> Oxidation of phenol and <Emphasis Type="Italic">o</Emphasis>-aminophenol in the channels of 3d-supramolecular coordination polymers

The host attractive properties of supramolecular coordination polymers of the type _￥³ _\infty^3 [(R₃Sn)₃FeIII(CN)₆], where R = methyl (I), n-butyl (II), and phenyl (III), afford the ability to be used as effective oxidizing reagents for phenol and o-aminophenol forming new host-guest supramolecular coordination polymers. Phenol was oxidized to 1,4-benzoquinone while o-aminophenol was oxidized to poly-o-aminophenol by the polymers I and II and to 2-aminophenoxazin-3-one by the polymer III. The oxidation products were investigated by methods of spectroscopy and high-performance liquid chromatography. The redox reactions were characterized by first-order kinetics. Moreover, mechanisms of the oxidation processes of phenol and o-aminophenol have been proposed.     

New approach for evaluation optical absorption measurements of charge transfer complexes between dimethoxynaphthalenes and tetracyanoethylene: singular value decomposition method

Singular-value decomposition (SVD) method is a numerical multidimensional technique appropriate for evaluation of optical absorption measurements of 1:1 charge transfer complexes (CTCs). Matrix algebra of the absorption data for different solutions and wavenumbers is primarily used for evaluation of the equilibrium constant and to obtain some general expressions to illustrate physical significance of the results obtained. The influence of the ratio of the concentrations of donor and acceptor is examined. It can lead to information about the stoichiometry of the complex formed in solution. Calculations on data for CTCs between dimethoxynaphthalene (DMNs) and tetracyanoethylene (TCNE) in CH2Cl2 at various temperatures are described. The results suggest that there is a noticeable difference in the K4, caused by substitutions at alpha- and beta-positions, because the alpha-position of naphthalene exhibits relatively high electron density compared with the corresponding beta-position. There is a linear correlation between the donor HOMO energy and charge-transfer absorption maxima.     

Paramagnetic charge-transfer guest–host coordination polymers. Thiophene compounds encapsulated within the channels of the three-dimensional coordination polymers [(R3Sn)3Fe(CN)6] n,R = Me,n-Bu or Ph

Various thiophene compounds have been shown to be encapsulated and partly oxidized within the channels of the three-dimensional (3D) host coordination polymers [(R₃Sn)₃Fe(CN)₆] _n (R = Me, n-Bu or Ph) to give guest–host encapsulated systems. The structure and physical properties of these systems were studied by X-ray powder diffraction, i.r., u.v.–vis., e.p.r. spectra and magnetic measurements. Thiophene compounds do not polymerize within the channels of the host, but rather give paramagnetic charge-transfer guest–host systems.     

Polarographic analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III)

The analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III) and 1 M H₂SO₄ are investigated using the polarographic technique. The wave corresponding to the reduction of Fe(III) to Fe(II) was found to be completely suppressed by the addition of 1% pyrogallol. Thus, different mixtures of these elements, viz. Hg(II), Cu(II), Cd(II), As(III) and Fe(III)-mixture (A), Cu(II), Cd(II), Sb(III), As(III) and Fe(III)-mixture (B), and Cu(II), Cd(II), Ti(IV), U(VI) and Fe(III)-mixture (C), were quantitatively determined using 1% pyrogallol and 1 M H₂SO₄ as supporting electrolyte. The i₁/c results give excellent correlations in each case, as indicated from the results of leastsquares regression analysis.     

NOVEL SUPRAMOLECULAR DERIVATIVES CONTAINING TWO R3Sn+ (R = Me,n-Bu,or Ph) CONNECTING UNITS: THE FORMATION OF NOVEL HOST–GUEST SYSTEMS BY THE FACILE ENCAPSULATION OF GUEST THIOPHENE COMPOUNDS

New supramolecular complexes [(Me ₃ Sn)(Ph ₃ Sn) ₂ Fe(CN) ₆ ] (I) and [(n-Bu ₃ Sn)(Ph ₃ Sn) ₂ Fe(CN) ₆ ] (II) are readily accessible by straightforward self-assembly of [Fe(CN) ₆ ] ^3? and hydrated R ₃ Sn⁺/R′ ₃ Sn ⁺ ions (R = Ph, and R′ = Me or n-Bu). The structural characterization of (I) and (II) is compared with well-documented supramolecular complex containing only Ph ₃ Sn ⁺ unit, [(Ph ₃ Sn) ₃ Fe(CN) ₆ ]. These novel compounds have wide internal cavities capable of encapsulating voluminous organic compounds, and they behave as host acceptors forming charge transfer complexes (CTC). Thiophene compounds acting as guest donor species are encapsulated within the cavities of the three-dimensional (3D) supramolecular hosts. The structure and physical properties of these hosts and host–guest systems were studied by X-ray powder diffraction, IR, UV/Vis., and magnetic measurements.