Exfoliated nanosheets as a new strong solid acid catalyst

Two-dimensional metal oxide sheets in HTiNbO(5) and HSr(2)Nb(3)O(10), cation-exchangeable layered metal oxides, were examined as solid acid catalysts. Exfoliation of HTiNbO(5) and HSr(2)Nb(3)O(10) in aqueous solutions formed colloidal single-crystal TiNbO(5)(-) and Sr(2)Nb(3)O(10)(-) nanosheets, which precipitated under an acidic condition to form aggregates of HTiNbO(5) nanosheets and HSr(2)Nb(3)O(10) nanosheets. Although esterification of acetic acid, cracking of cumene, and dehydration of 2-propanol were not catalyzed by original HTiNbO(5) because of the narrow interlayer distance, which prevents the insertion of organic molecules, HTiNbO(5) nanosheets functioned as a strong solid acid catalyst for the reactions. Nanosheets of HSr(2)Nb(3)O(10) exhibited no or slight catalytic activity for these reactions. NH(3) temperature-programmed desorption and (1)H magic-angle spinning nuclear magnetic resonance spectroscopy revealed that HTiNbO(5) nanosheets have strong Br?nsted acid sites, whereas HSr(2)Nb(3)O(10) nanosheets do not.     

A strategy for the assembly of multiple porphyrin arrays based on the coordination chemistry of Ru-centered porphyrin pentamers.

An approach which employs pentameric porphyrin arrays as building blocks toward larger porphyrin arrays is described. Two flexible, and one relatively rigid, Ru-centered porphyrin pentamers (1-3) were synthesized and fully characterized. Their potential as building blocks toward larger porphyrin arrays has been studied via their coordination chemistry using bidentate and tetradentate ligands. DABCO (diazabicyclo[2.2.2]octane) can bind two monomeric porphyrins but was found to be too small to allow the complete formation of a 10-porphyrin array. On the other hand, titration of a larger bridging dipyridyl porphyrin ligand 17 (0.5 equiv) with 1 or 2 and tetrapyridyl ligand 18 (0.25 equiv) with 3 results in the formation of the 11-porphyrin and 21-porphyrin arrays, respectively, with the 21-porphyrin array containing porphyrins in three different metalation states. Changes in the chemical shift of the inner NH protons as well as the ortho- and meso-protons of the pyridyl groups of the porphyrin ligand clearly indicate the formation of large multiple porphyrin complexes. These studies demonstrate that by use of carefully designed building blocks and suitable bridging ligands, porphyrin arrays can be constructed with a dramatic increase in size in relatively few steps. Exploiting the fact that the strength of binding of pyridyl ligands is Ru > Zn > Ni, intra- vs intermolecular competition has been used to investigate aspects of the folding of the array. The photophysical properties of 3 are also described.     

Chemical control of electronic structure and superconductivity in layered borides and borocarbides: understanding the absence of superconductivity in LixBC

The synthetic search for materials related to the 39 K superconductor MgB2 has been difficult. The most promising theoretical suggestion, hole doping of LiBC, does not lead to a new superconductor. We show here that a combination of density functional theory (DFT) calculations, materials synthesis, and structural characterization reveals the origin of the puzzling absence of superconductivity in Li1/2BC as a subtle change in the electronic structure driven by structural response to the introduction of holes. This indicates that the unique aspects of the electronic structure of MgB2 will be demanding to replicate in other systems.     

Molecular orientation by surface forces: I. On the replication of surface forces by plastic materials

We have attempted to replicate the surface electrical profile of freshly cleaved sodium chloride crystals using materials with known electret characteristics such as; polyethylene; polyvinyl acetate; polymethyl methacrylate; polyvinyl chloride; polystyrene and carnauba wax. Only P.V.C. replicas exhibit surface orientational properties. A theory is presented to account for the orientation of polar organic molecules on polyvinyl chloride replicas of sodium chloride surfaces and evidence is reported for the existence of long range surface forces arising from gross crystallographic defects.     

Study of the D(+)(s)-->pi(-)pi(+)pi(+) decay and measurement of f(0) masses and widths

From a sample of 848+/-44 D(+)(s)-->pi(-)pi(+)pi(+) decays, we find gamma(D(+)(s)-->pi(-)pi(+)pi(+))/gamma(D(+)(s)-->straight phipi(+)) = 0.245+/-0.028(+0.019)(-0.012). Using a Dalitz plot analysis of this three body decay, we find significant contributions from the channels rho(0)(770)pi(+), rho(0)(1450)pi(+), f(0)(980)pi(+), f(2)(1270)pi(+), and f(0)(1370)pi(+). We also present the values obtained for masses and widths of the resonances f(0)(980) and f(0)(1370).