Seamless Rim-Functionalization of h-BN with Silica-Experiment and Theoretical Modeling.

Boron nitride contains six-ring layers, which are isostructural to graphene, and it exhibits similar extraordinary mechanical strength. Unlike graphene, hexagonal boron nitride (h-BN) is an insulator and has some polar features that make it a perfect material for those applications graphene is not suitable for, for example, purely ionic conductors, insulating membranes, transparent coatings, composite ceramics, high oxidation resistance materials. We report here a selective rim-functionalization of h-BN with SiO2 by using the Stöber process. A closed, protruding ring of SiO2 is formed covering all edges perpendicular to the [001] zones of the h-BN stacks and thus shield the most reactive centers of BN layers. SEM and HAADF-STEM images, X-ray spectroscopy, and atomic force microscopy confirm the rim-functionalization by SiO2 . XRD demonstrates the absence of any intercalation phenomenon of BN and reveals the glassy nature of the SiO2 rims. Selected variations of synthesis and theoretical modeling both confirm that rim activation by water prior to the Stöber condensation is crucial. First-principles calculations also confirm that dangling bonds of clean BN edges merge to give interlayer bonds that make further functionalization much more difficult. The reported reaction pathway should allow for other new functionalizations of pure BN and of the rimmed SiO2 /h-BN composites.

Thermodynamics of core metal replacement and self-assembly of Ca(2+) 15-metallacrown-5.

The equilibria for core Ca(2+) replacement by Ln(3+) in copper(II) 15-MC-5 complexes have been investigated using a series of visible spectrophotometric titrations of calcium(II) metallacrowns ({Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+)) with Ln(3+) ions (H(2)L = pheha, (S)-alpha-phenylalaninehydroxamic acid, or trpha, (S)-alpha-tryptophanhydroxamic acid). These studies allowed the determination of the equilibrium constants for the reaction {Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+) + Ln(3+) --> {Ln(III)[15-MC(Cu(II)(N)(L))-5]}(3+) + Ca(2+) in methanol/water 9:1 (Ln(3+) = La(3+), Gd(3+), Dy(3+), Er(3+)) or 99:1 (Ln(3+) = La(3+), Nd(3+), Gd(3+), Dy(3+), Er(3+), Yb(3+)), respectively. The log K for these reactions decreases with increasing atomic number of the lanthanide(III), ranging from 6.1 to 3.91 in methanol/water 9:1. The same behavior is observed in methanol/water 99:1, although the constants are uniformly lower (log K = 4.09-2.52). A significant thermodynamic selectivity was observed for the later lanthanides (Gd(3+)-Yb(3+)) while a smaller selectivity is present throughout the beginning of the series (La(3+)-Gd(3+)). This observation has been interpreted on the basis of the size correspondence between the metal ions and the metallacrown cavity. The overall stability of the {Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+) in methanol/water 9:1 has been determined by pH-spectrophotometric titrations with HCl. The resulting log K values are 63.46(12) and 65.05(13) for pheha and trpha, respectively (Ca(2+) + 5Cu(2+) + 5HL(-) = {Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+) +5H(+)). The stability of both the La(3+) and Ca(2+) 15-metallacrown-5 complexes in the presence of high Na(+) concentrations has also been demonstrated by spectophotometric studies. Based upon these observations, the preference of the 15-MC-5 for Ca(2+) complexation compared to crown ethers has been quantitatively demonstrated for the first time.