Dimethylaluminum and gallium amino alkoxides

An S,S′-thioether—thioester chelating ligand [7,8-μ-SCH₂C(O)S-7,8-C₂B₉H₁₀]⁻ (L₁), incorporating the unit [—(C)₂B₉H₁₀]⁻ has been synthesized. Reactions have been conducted with RhCl(PPh₃)₃ and PdCl₂(PPh₃)₂ complexes in ethanol. With Rh, L₁ maintains its original cyclic nature and most probably chelation via thioether—thioester takes place. The carborane negative charge may stabilize this original thioether—thioester complex. The other two Rh positions are occupied by two PPh₃ ancillary ligands forming [Rh(L₁)(PPh₃)₂]. The reaction of L₁ with Pd induces ligand modifications and the cyclic nature of L₁ is lost. A transesterification process leading to a dianionic ligand L₂, [7-S-8-SCH₂C(O)OCH₂CH₃−7,8-C₂B₉H₁₀]²⁻ has taken place. In this way L₂ is capable of compensating the dipositive Pd charge. The other two Pd positions are occupied by two PPh₃. This reaction has been extended to methanol and isopropanol solvents. The crystal structure of [Pd(L₂)(PPh₃)₂] has been determined.     

Neutron scattering in polymer gels at the theta temperature

Small angle elastic neutron scattering was performed on three polystyrene networks swollen to equilibrium in cyclohexane at the theta temperature. Comparison of the SANS spectra with similar measurements in uncross-linked solutions reveals that in the intermediate Q region the gels behave like solutions of lower concentration than the equivalent solutions. We assume that the gel spectra are composed of a static component plus a dynamic, or solution-like part. By a suitable fitting procedure, the former can be estimated, yielding the mean square static concentration fluctuation <Δφ²> generated by cross-linking contraints in the gel. Independent measurement of the swelling pressure of these gels permits an estimate to be made of the scattering intensity I(Q=0) of the dynamic part of the spectrum. Plausible agreement is found between the macroscopic and microscopic estimations of the osmotic compressibility if allowance is made for the concentration polydispersity in the gels.     

Charge‐transfer character of halogen bonding: Molecular structures and electronic spectroscopy of carbon tetrabromide and bromoform complexes with organic σ‐ and π‐donors

Carbon tetrabromide and bromoform are employed as prototypical electron acceptors to demonstrate the charge‐transfer nature of various intermolecular complexes with three different structural types of electron donors represented by (1) halide and pseudohalide anions, (2) aromatic (π‐bonding) hydrocarbons, and (3) aromatics with (n‐bonding) oxygen or nitrogen centers. UV–Vis spectroscopy identifies the electronic transition inherent to such [1:1] complexes; and their Mulliken correlation with the donor/acceptor strength verifies the relevant charge‐transfer character. X‐ray crystallography of CBr₄/HCBr₃ complexes with different types of donors establishes the principal structural features of halogen bonding. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:449–459, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20264     

Quasi-elastic neutron scattering in gels and solutions

Measurements of swelling pressure, neutron spin-echo scattering, and dynamic light scattering were made in an end-linked poly(dimethylsiloxane) (PDMS) gel swollen to equilibrium in a good solvent (toluene) and also in the equivalent solution. The macroscopic osmotic modulus is depressed in the gel. Neutron spin echo observations at intermediate and high values of the scattering vector Q reveal that the mobility of the monomers is unaffected by cross-linking. Elastic neutron scattering at small Q detects non-uniformities in the polymer concentration distribution, which are absent from the solution. These non-uniformities play a major role in the dynamic response of the system at lower Q, and and appear to be the cause of the observed reduction in osmotic pressure.     

Calcium induced volume transition in polyelectrolyte gels

The osmotic properties and the small angle neutron scattering (SANS) behaviour of fully neutralized sodium polyacrylate gels are investigated in the presence of calcium ions. Analysis of the SANS response displays three characteristic length scales, two of which are of thermodynamic origin, while the third, associated with the frozen-in structural inhomogeneities, is static. The SANS results are consistent with direct osmotic observations which indicate that the thermodynamic properties cannot be adequately described by a single correlation length. The concentration dependence of the osmotic pressure displays a power law behaviour with an exponent that decreases with increasing calcium concentration.     

Ion condensation in a polyelectrolyte gel

Anomalous small angle X-ray scattering is used to determine the distribution of divalent ions in a neutralized polyelectrolyte gel of sodium polyacrylate in the vicinity of the volume transition. At the five different energies of the incident beam used to vary the contrast, the scattering curves have similar shapes, and are separated only by constant multiplying factors. This result, in conjunction with SANS results from the same sample, indicates that the divalent ion (strontium) is confined on the polymer backbone.