Effect of the superconducting transition on phonon energies and lifetimes in lead

We have performed a high-resolution inelastic neutron scattering study of certain transverse phonons in lead. We find that neither the energies nor the linewidths change appreciably with the onset of superconductivity. This finding contradicts a recent experimental report, but is in accord with theoretical expectations.     

Glaser-mediated synthesis and photophysical characterization of diphenylbutadiyne-linked porphyrin dyads

The Pd-mediated Glaser coupling of a zinc monoethynyl porphyrin and a magnesium monoethynyl porphyrin affords a mixture of three 4,4'-diphenylbutadiyne-linked dyads comprised of two zinc porphyrins (Zn-pbp-Zn), two magnesium porphyrins (Mg-pbp-Mg), and one metalloporphyrin of each type (Zn-pbp-Mg). The latter is easily isolated due to the greater polarity of the magnesium versus the zinc chelate. Exposure of Zn-pbp-Mg to silica gel results in selective demetalation, affording Zn-pbp-Fb where Fb = free base porphyrin. This synthesis route employs the magnesium porphyrin as a latent form of the Fb porphyrin, thereby avoiding copper insertion during the Glaser reaction, and as a polar entity facilitating separation. The absorption spectrum of Zn-pbp-Mg or Zn-pbp-Fb is the sum of the spectra of the component parts, while in each case the fluorescence spectrum upon illumination of the Zn porphyrin is dominated by emission from the Mg or Fb porphyrin. Time-resolved absorption spectroscopy shows that the energy-transfer rate constants are (11 ps)(-1) and (37 ps)(-1) for Zn-pbp-Mg and Zn-pbp-Fb, respectively, corresponding to energy-transfer quantum yields of 0.995 and 0.983, respectively. The calculated F?rster through-space rates are (1900 ps)(-1) and (1100 ps)(-1) for Zn-pbp-Mg and Zn-pbp-Fb, respectively. Accordingly, the through-bond process dominates for both dyads with a through-bond:through-space energy-transfer ratio of > or =97:1. Collectively, the studies show that the 4,4'-diphenylbutadiynyl linker supports fast and efficient energy transfer between Zn and Mg or Fb porphyrins.     

Self‐Cleaning and Next Generation Anti‐Fog Surfaces and Coatings

Due to their high surface energy, hydrophilic surfaces are susceptible to contaminations which are difficult to remove and often ruin the surface. Traditional anti‐fog coatings are especially limited by contaminants, as the prevention of fogging is enhanced as hydrophilicity increases. Thus, advanced solutions to fogging are required which incorporate some degree of self‐cleaning ability without significant losses in anti‐fog character. Potential next generation anti‐fog surfaces are characterized with particular emphasis on extended lifetime stimuli‐responsive surfaces. Surfactant‐based surfaces exhibited simultaneous hydrophilicity, necessary for anti‐fogging, and oleophobicity, necessary for contamination resistance. The combination of these features rendered the surface as self‐cleaning.

     

Pressure dependence of the rotational ground state tunnel splitting in Ni(NH3)6I2

Inelastic neutron scattering techniques have been used to determine the rotational tunnel splitting of the librational ground state of ammonia molecules in Ni(NH₃)₆I₂ as a function of hydrostatic pressure up to 5.6 kbar at 8 K. The resulting exponential dependence of the tunnel splitting on pressure was interpreted with the help of a concurrent measurement of the compressibility to suggest a dependence on the interatomic distance as r^?9 of the orientational potential. The phase transition temperature at 5.6 kbar was determined to be 27 K compared with 19.9 K at atmospheric pressure.     

Synthesis of a new trans-A2B2 phthalocyanine motif as a building block for rodlike phthalocyanine polymers

Polyphthalocyanines have potential application in the development of electronic materials. One-dimensional polyphthalocyanines are accessible through monomers having a trans-A2B2 structure, but the preparation of a truly linear polyphthalocyanine is challenging because of limitations imposed by the geometry of phthalocyanines and the methodology for their synthesis. Benzimidazoporphyrazines are a known class of extra-annulated phthalocyanines. A trans-A2B2 benzimidazoporphyrazine is geometrically suitable for the preparation of rodlike polymers. A new synthesis of benzimidazoporphyrazines is presented as a stepping stone to the synthesis of trans-A2B2 benzimidazoporphyrazines.