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    Synthesis and Recognition Properties of Higher Order Tetrathiafulvalene (Ttf) Calix N Pyrroles (N=4-6)

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    Two new benzoTTF-annulated calix[n]pyrroles (n = 5 and 6) were synthesized via a one-step acid catalyzed condensation reaction and fully characterized via single crystallographic analyses. As compared to the known tetra-TTF annulated calix[4]pyrrole, which is also produced under the conditions of the condensation reaction, the expanded calix[n]pyrroles (n = 5 and 6) are characterized by a larger cavity size and a higher number of TTF units (albeit the same empirical formula). Analysis of the binding isotherms obtained from UV-Vis spectroscopic titrations carried out in CHCl3 in the presence of both anionic (Cl-, Br-, I-, CH3COO-, H2PO4-, and HSO4-) and neutral (1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT)) substrates revealed that as a general rule the calix[6]pyrrole derivative proved to be the most efficient molecular receptor for anions, while the calix[4]pyrrole congener proves most effective for the recognition of TNB and TNT. These findings are rationalized in terms of the number of electron rich TTF subunits and NH hydrogen bond donor groups within the series, as well as an ability to adopt conformations suitable for substrate recognition, and are supported by solid state structural analyses.National Science Foundation CHE 1057904, 0741973Robert A. Welch Foundation F-1018Danish Natural Science Research Council (FNU) 272-08-0047, 11-106744WCU (World Class University) program of Korea R32-2010-10217-0Villum FoundationChemistr

    Dielectric study of the glass transition: correlation with calorimetric data

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    The glass transition in amorphous poly(ethylene terephthalate) is studied by thermally stimulated depolarization currents (TSDC) and differential scanning calorimetry (DSC). The ability of TSDC to decompose a distributed relaxation, as the glass transition, into its elementary components is demonstrated. Two polarization techniques, windows polarization (WP) and non-isothermal windows polarization (NIW), are employed to assess the influence of thermal history in the results. The Tool-Narayanaswami-Moynihan (TNM) model has been used to fit the TSDC spectra. The most important contributions to the relaxation comes from modes with non-linearity (x) around 0.7. Activation energies yield by this model are located around 1eV for polarization temperature (Tp) below 50C and they raise up to values higher than 8eV as Tp increases (up to 80C). There are few differences between results obtained with WP and NIW but, nonetheless, these are discussed. The obtained kinetic parameters are tested against DSC results in several conditions. Calculated DSC curves at several cooling and heating rates can reproduce qualitatively experimental DSC results. These results also demonstrate that modelization of the non-equilibrium kinetics involved in TSDC spectroscopy is a useful experimental tool for glass transition studies in polar polymers.Comment: 13 pages, 2 tables, 10 figures; minor change
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