Identification of the cobalt(II) chloride ‘mixed’ solvate Co4Cl8(H2O)4(MeCN)6: the ionic structure trans-[Co(H2O)2(MeCN)4] trans-[Co(H2O)2(MeCN)2(CoCl4)2]

The structure of the title compound features mononuclear octahedral Co^II cations, trans-[Co(H₂O)₂(MeCN)₄]²⁺, and trinuclear anions, trans-[Co(H₂O)₂(MeCN)₂(CoCl₄)₂]^2–; the latter centrosymmetric units contain a central octahedral Co(H₂O)₂(MeCN)₂ moiety with two tetrahedral [CoCl₄]^2– ligands. These two large ions are held in a network of intra- and inter-molecular hydrogen bonding.     

Two isomorphous complexes: di­chloro­[phthalocyaninato(2–)]­tin(IV) and di­chloro­[phthalocyaninato(2–)]­germanium(IV)

Isomorphous triclinic forms of di­chloro­[phthalocyaninato(2−)]­tin(IV), [Sn(C₃₂H₁₆N₈)Cl₂], and di­chloro­[phthalocyaninato(2−)]­ger­manium(IV), [Sn(C₃₂H₁₆N₈)Cl₂], and a monoclinic form of the latter have been obtained from the reaction of pure tin and germanium powder, respectively, with phthalo­nitrile under a stream of ICl vapour. All three crystal structures consist of centrosymmetric [SnPcCl₂] and [GePcCl₂] [Pc is phthalocyaninate(2−)] mol­ecules, which are separated but interacting. In the triclinic forms (Sn and Ge), the Pc macrocycles are not staggered but slipped, and in the monoclinic form (Ge), the mol­ecules are additionally inclined. In both cases, the central Sn or Ge atom is six‐coordinated by the four iso­indole N atoms of the Pc macrocyclic ligand and by two Cl atoms (located trans) into a tetragonal–bipyramidal structure. The arrangement of [SnPcCl₂] and [GePcCl₂] mol­ecules in the crystal structure is determined mainly by intermolecular C—H⃛Cl, π–π and van der Waals interactions.     

Microstructure of triblock copolymers in asphalt oligomers

A model asphalt has been separated into two parts, asphaltene and maltene, through solvent extraction by n-heptane. The interactions of asphaltene and maltene with the triblock copolymer poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) were investigated by transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), dynamic mechanical analysis (DMA), and differential scanning calorimetry (DSC). Asphaltene was found to be essentially immiscible with both blocks of SEBS, while maltene was miscible with SEBS. An unusual sequence of morphological transformations of SEBS microstructure with respect to the addition of maltene was observed. The morphology transformed from hexagonal cylinder, to perforated layers, to lamellae and then back to the original hexagonal cylinder. The observed transformation reflects a limited solubility for both S and EB domains: at lower concentration maltene is a preferential additive for S domains, while increasing concentration the swelling of EB-rich microdomains by maltene becomes significant. The basic understanding of the interactions of the components of asphalt with SEBS gives a simple path to characterize and predict the microstructure of triblock copolymers in asphalt oligomers. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2857–2877, 1997     

Directly Bound Deuterons Increase X-Nuclei Hyperpolarization using Dynamic Nuclear Polarization

Deuterated ¹³C sites in sugars (D-glucose and 2-deoxy-D-glucose) showed 6.3-to-17.5-fold higher solid-state dynamic nuclear polarization (DNP) levels than their respective protonated sites at 3.35T. This effect was found to be unrelated to the protonation of the bath. Deuterated ¹⁵N in sites bound to exchangeable protons ([¹⁵N₂]urea) showed a 1.3-fold higher polarization than their respective protonated sites at the same magnetic field. This relatively smaller effect was attributed to incomplete deuteration of the ¹⁵N sites due to the solvent mixture. For a ¹⁵N site that is not bound to protons or deuterons ([¹⁵N]nitrate), deuteration of the bath did not affect the polarization level. These findings suggest a phenomenon related to DNP of X-nuclei directly bound to deuteron(s) as opposed to proton(s). It appears that direct binding to deuterons increases the solid-state DNP polarization level of X-nuclei which are otherwise bound to protons.     

ChemInform Abstract: Structural and Electrochemical Study od a New Crystalline Hydrate Iron(III) Phosphate FePO4·H2O Obtained from LiFePO4(OH) by Ion Exchange.

FePO₄·H₂O is prepared by Li⁺/H⁺ exchange from an aqueous HNO₃ suspension of LiFePO₄(OH) at about 60 °C.