Self‐assembly of π‐conjugated bis(terpyridine) ligands with zinc(II) ions: New metallosupramolecular materials for optoelectronic applications

A series of main‐chain metallopolymers ( P1–P10 ) was prepared by the self‐assembly of rigid‐linear π‐conjugated bis(terpyridine) monomers ( 1–10 ) with Zn^II ions and was fully characterized. The polymerization was additionally confirmed by UV/vis titration experiments. A strong increase in viscosities (around 1.6 times) relative to those of the monomer solutions was found. The thermal stability of P1–P10 compared with that of 1–10 was enhanced as a result of the metallopolymerization. The electro‐optical properties of the materials were investigated in detail. Tuning of the electrochemical and photophysical properties was enabled; thus, bright purple to green photoluminescent (PL) emission (PL quantum yields of 0.12–0.81) for P1–P10 was observed in solution with the emission color strongly depending on the nature of the π‐conjugated bis(terpyridine) system. Thin homogeneous films of P6 were prepared by solution processing, that is, spin‐coating and inkjet‐printing, and exhibited intense yellow PL emission in the solid state. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4083–4098, 2009     

Polyamido amine dendrimers functionalized with poly(phenylenevinylene) dendrons at their periphery

A series of polyamido amine (PAMAM) dendrimers (Generations 2, 3, 4, and 6) fully functionalized at their periphery with first‐ and second‐generation poly (phenylenevinylene) (PPV) dendrons have been efficiently prepared. MALDI‐TOF mass spectrometry proved to be particularly useful for the characterization of the new hybrid dendrimers as well as for the estimation of the average number of PPV dendrons attached to the surface. The optical absorption and emission properties of these systems were studied. The materials display extremely high molar extinction coefficients and emit blue light with only slightly lower fluorescence quantum yields than the corresponding free dendrons. Self‐quenching interactions between PPV units were not observed in THF. However, the luminescence properties underwent a dramatic change when toluene was used as the solvent. The lower polarity of toluene caused shrinkage of the PAMAM structure and brought the PPV chromophores closer together, leading to self‐quenching interactions and excimer formation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6409–6419, 2009     

Anomalies and proximity effect in high-T C tunnel junctions

Summary Some of the main anomalies in conductance characteristics of high-T _C tunnel junctions are considered. Mainly, the extreme, depression of gap structures, the presence of conductance peaks in corrispondence to the counterelectrode gap, and ?zero-bias anomalies? will be examined. The possibility of application of the proximity McMillan model to describe the behaviour in conductance of high-T _C junctions is considered. Discussion and preliminary comparison with experimental data on YBCO junctions are also reported.     

An eco-friendly tandem tosylation/Ferrier N-glycosylation of amines catalyzed by Er(OTf)3 in 2-MeTHF

Er(OTf)₃ in 2-MeTHF provides a new and eco-friendly process for Ferrier glycosylation of sulfonamides and amino acids with various N-nucleophiles.The stereoselective synthesis of 2,3-unsaturated-N-pseudoglycals was carried out with 3,4,6-tri-O-acetyl-d-glucal and different nucleophiles affording good results in a short time.     

Molecular imprinting polymerization by Fenton reaction

The aim of this study is the preparation of molecularly imprinted polymers by employing a redox pair as initiator system. Bulk molecularly imprinted polymers were synthesized by using Fenton reagents as initiator system. Theophylline, methacrylic acid, and ethylene glycol dimethacrylate were employed as model template, functional monomer, and crosslinking agent, respectively. Conventional imprinted polymers were also prepared by using 2,2′-azoisobutyronitrile in order to evaluate the efficiency of the proposed initiator system. Redox molecularly imprinted polymers and conventional molecularly imprinted polymers were characterized by water uptake measurement, while the imprinting effect of synthesized polymers were evaluated by performing binding experiments in organic (acetonitrile) and in water (buffered water solution at pH = 7.4) media.     

Exploring the emissive properties of new azacrown compounds bearing aryl, furyl, or thienyl moieties: a special case of chelation enhancement of fluorescence upon interaction with Ca(2+), Cu(2+), or Ni(2+)

Three new compounds bearing furyl, aryl, or thienyl moieties linked to an imidazo-crown ether system (1, 2, and 3) were synthesized and fully characterized by elemental analysis, infrared, UV-vis absorption, and emission spectroscopy, X-ray crystal diffraction, and MALDI-TOF-MS spectrometry. The interaction toward metal ions (Ca(2+), Cu(2+), Ni(2+), and Hg(2+)) and F(-) has been explored in solution by absorption and fluorescence spectroscopy. Mononuclear and binuclear metal complexes using Cu(2+) or Hg(2+) as metal centers have been synthesized and characterized. Compounds 2 and 3 show a noticeable enhancement of the fluorescence intensity in the presence of Ca(2+) and Cu(2+) ions. Moreover compound 3 presents a dual sensory detection way by modification of the fluorimetric and colorimetric properties in the presence of Cu(2+) or Hg(2+). EPR studies in frozen solution and in microcrystalline state of the dinuclear Cu(II)3 complex revealed the presence of an unique Cu(2+) type.     

Montmorillonite K-10 clay catalyzed solvent-free synthesis of bis-indolylindane-1,3-dione, 2-(1′,3′-dihydro-1H-[2,3′]biindolyl-2′-ylidene)-indan-1,3-dione and bisindolylindeno[1,2-b]quinoxaline under microwave irradiation

An environmentally benign protocol has been described for the synthesis of novel 2-(1′,3′-dihydro-1H-[2,3′]biindolyl-2′-ylidene)-indan-1,3-diones/bis-indolylindane-1,3-diones from ninhydrin and 3-substituted/unsubstituted indoles. It uses montmorillonite K-10 as catalyst in a solvent-free condition under microwave irradiation. The method was also used for the synthesis of novel bisindolylindeno[1,2-b]quinoxaline derivatives.     

High molar mass silicone rubber reinforced with montmorillonite clay masterbatches: Morphology and mechanical properties

Rubber composites were obtained from natural (MT) or organomodified (O-MT) montmorillonite clay masterbatches and high molar mass poly(dimethylsiloxane)-gum (PDMS). The masterbatches were prepared by compounding MT or O-MT with a siloxane-polyether surfactant. The rubber composites were characterized by X-ray diffraction, small angle/wide angle X-ray scattering, scanning and transmission electron microscopies and tensile tests. The results showed that masterbatch compounding with O-MT improved the dispersion of this clay into the PDMS matrix. The morphology of the resulting composite showed a combination of intercalated and partially exfoliated clay layers with occasional clay aggregates. The addition of only 5 phr of O-MT into the PDMS matrix, via masterbatch compounding, improved the tensile strength as much as that obtained with the composite filled with 30 phr of O-MT clay prepared by the direct addition of the clay to PDMS. Moreover, the elongation at break was improved by at least 126%.     

High-pressure vibrational properties of polyethylene

The pressure evolution of the vibrational spectrum of polyethylene was investigated up to 50 GPa along different isotherms by Fourier-transform infrared and Raman spectroscopy and at 0 K by density-functional theory calculations. The infrared data allow for the detection of the orthorhombic Pnam to monoclinic P2(1)∕m phase transition which is characterized by a strong hysteresis both on compression and decompression experiments. However, an upper and lower boundary for the transition pressure are identified. An even more pronounced hysteresis is observed for the higher-pressure transition to the monoclinic A2/m phase. The hysteresis does not allow in this case the determination of a well defined P-T transition line. The ambient structural properties of polyethylene are fully recovered after compression/decompression cycles indicating that the polymer is structurally and chemically stable up to 50 GPa. A phase diagram of polyethylene up to 50 GPa and 650 K is proposed. Analysis of the pressure evolution of the Davydov splittings and of the anomalous intensification with pressure of the IR active wagging mode provides insight about the nature of the intermolecular interactions in crystalline polyethylene.     

A Water Sensitive Hydrate: The Bis‐Catena Complex Salt [Mn(H2O)6][BiI4]2·2H2O

Bright red crystals of [Mn(H₂O)₆][BiI₄]₂ · 2H₂O are obtained from a solution of MnI₂, BiI₃, and I₂ in absolute ethanol, which is exposed to humid air. Reversible dehydratization sets in at about 50 °C. Added water decomposes the hydrate by irreversible precipitation of BiOI. The optical bandgap is about 1.9(1) eV. X‐ray diffraction on a single‐crystal revealed a monoclinic lattice (space group P2₁/c) with a = 760.39(4) pm, b = 1315.6(1) pm, c = 1398.37(7) pm, and β = 97.438(4)°. In the crystal structure zigzag chains of edge‐sharing [BiI_2/1I_4/2]^– octahedra and linear strings of H₂O‐bridged [Mn(H₂O)₆]²⁺ octahedra run parallel [100].