“Living” free radical graft copolymers I: Preparation and properties

Polymers substituted with thio groups are useful for the photochemical synthesis of graft copolymers. Such copolymers have been prepared by the initial conversion of backbone polymers containing chlorinated substituents into polymers containing diethyldithiocarbamate (TC), isopropyl xanthate (IX) or mercaptobenzothiazole (BT) functionality. The photochemical reaction of monomers with these products produced graft copolymers. A variety of halogenated polymers were investigated as starting materials for these syntheses, including poly(vinyl chloride), chlorinated polyvinyl chloride), chlorinated polyethylene, chlorobutyl rubber and neoprene. Characteristics of the grafting reactions, including “pseudo-living” behavior and tandem grafting aspects, were investigated. Glass transitions of the grafted polymers were found to vary uniformly with composition for most of the grafted products.     

Comparison of irreversible and reversible cluster formation

Covalent and reversible cluster molecules were synthesized by an A₃B₂ type gelation. Crosslinking of three-arm hydroxyl-terminated star polymers with 2,4-toluenediisocyanate gave branched polymers, while the reversible analogue was made by crosslinking of tertiary amine-terminated star polymers with bis(4-hydroxy-3,5-dinitrophenyl) adipate. Gelation process was followed by static and dynamic light scattering. The extent of reacted groups was measured with UV spectroscopy. Growth of the covalent clusters could be described in terms of percolation scaling laws. The experimental gel point (P_{OH, cr} = 0.70) was shifted significantly from the theoretical predicted gel point (P_{OH, cr} = 0.50), indicating extensive ring formation during the gelation. The reversible endlinking reaction gave no macroscopic gelation, though increase of the cluster dimensions was observed. Ring formation proved to be an important side reaction in both cases; however, the ring formation ability seems to change in a different manner during the course of a gelation.     

Spin-transition in nearly cubic site in [FeII(L)3][PF6]2

The spin-transition (¹A₁?⁵T₂) behaviour of a new mononuclear iron(II) compound [Fe^II(L)₃][PF₆]₂[L = 2-[3-(2′-pyridyl)pyrazole-1-ylmethyl]pyridine] has been investigated by ⁵⁷Fe Mössbauer spectroscopy. Analysis of the Mössbauer spectra revealed low value of the quadrupole splitting of the high-spin state which reflects iron(II) to be in nearly cubic lattice site. Mössbauer spectra under light show the light-induced excited spin state trapping effect and the observed quadrupole splitting of the metastable high-spin state is found little sensitive to the high-spin fraction value. DFT calculations are in progress to document the almost cubic nature of the ligand-field acting on the iron atom.     

Synthesis and Hydrogen-Bond Patterns of Aryl-Group Substituted Silanediols and -triols from Alkoxy- and Chlorosilanes

Organosilanols typically show a high condensation tendency and only exist as stable isolable molecules under very specific steric and electronic conditions at the silicon atom. In the present work, various novel representatives of this class of compounds were synthesized by hydrolysis of alkoxy- or chlorosilanes. Phenyl, 1-naphthyl, and 9-phenanthrenyl substituents at the silicon atom were applied to systematically study the influence of the aromatic substituents on the structure and reactivity of the compounds. Chemical shifts in ²⁹Si NMR spectroscopy in solution, correlated well with the expected electronic situation induced by the substitution pattern on the Si atom. ¹H NMR studies allowed the detection of strong intermolecular hydrogen bonds. Single-crystal X-ray structures of the alkoxides and the chlorosilanes are dominated by π-π interactions of the aromatic systems, which are substituted by strong hydrogen bonding interactions representing various structural motifs in the respective silanol structures.     

An expedient reductive method for conversion of ketoximes to the corresponding carbonyl compounds

A wide array of readily prepared pivalates of ketoximes can be converted to the corresponding ketones in good yields by treatment with iron powder in THF containing catalytic amounts of both trimethylsilyl chloride and glacial acetic acid at room temperature for 30 min, followed by a brief aqueous workup.     

The Least-Perimeter Partition of a Sphere into Four Equal Areas

We prove that the least-perimeter partition of the sphere into four regions of equal area is a tetrahedral partition.