Acyclic catena-diphosphinodiphosphonium dications [R3P-PR'-PR'-PR3]2+ or bisphosphine-diphosphenium complexes [R3PPR'-PR'PR3]2+: synthesis by reductive P-P coupling of [R3P-PR'Cl]+ and phosphine ligand exchange

The acyclic tetraphosphorus dication [Ph3P-PPh-PPh-PPh3]2+ has been formed by the reductive coupling of [Ph3P-PPhCl]+, providing a new synthetic method for the systematic development of catena-phosphorus cations. Ligand exchange (Ph3P for Me3P) gives [Me3P-PPh-PPh-PMe3]2+, implicating these dications as bisphosphine-diphosphenium complexes.     

Conformational disorder of conjugated polymers

Conformational disorder of conjugated polymers is an important issue to be understood and quantified. In this paper we present a new method to assess the chain conformation of conjugated polymers based on measurements of intrachain energy transfer. The chain conformation is modeled on the basis of monomer-monomer interactions, such as torsion, bending, and stretching of the connecting bond. The latter two potentials are assumed to be harmonic, while the torsional potential was calculated by density functional theory using B3-LYP functional with the SVP basis set. The energy transfer dynamics of excitons on these chains are quantitatively simulated using Forster-type line-dipole energy transfer. This allows us to compare the simulated ground state conformation of single polymer chains to ultrafast depolarization experiments of poly [3-(2,5-dioctylphenyl)thiophene] in solution. We identify torsional rotation as the main contributor to conformational disorder and find that this disorder is mainly controlled by the energy difference between syn and anti bonds.     

First-order metal-insulator transitions in manganites: are they universal?

Conductivity data for La(2-2x)Sr(1+2xMn2O7 (x = 0.6) show a first-order transition from an orbital- or charge-ordered insulator to a metal as the temperature falls below approximately 160 K. The change in conductivity is 100 times larger than that seen previously in any single-phase manganite in zero field. The metallic low-temperature state is similar to x = 0.58, but x = 0.58 shows no evidence of orbital or charge order. This result supports a conclusion that strongly coupled magnetic-conductive transitions are first order.     

Symmetric square L-values and dihedral congruences for cusp forms

Let be a prime, and k=(p+1)/2. In this paper we prove that two things happen if and only if the class number . One is the non-integrality at p of a certain trace of normalised critical values of symmetric square L-functions, of cuspidal Hecke eigenforms of level one and weight k. The other is the existence of such a form g whose Hecke eigenvalues satisfy “dihedral” congruences modulo a divisor of p (e.g. p=23, k=12, g=Δ). We use the Bloch-Kato conjecture to link these two phenomena, using the Galois interpretation of the congruences to produce global torsion elements which contribute to the denominator of the conjectural formula for an L-value. When , the trace turns out always to be a p-adic unit.     

On the Hausdorff and packing measures of typical compact metric spaces

We study the Hausdorff and packing measures of typical compact metric spaces belonging to the Gromov–Hausdorff space (of all compact metric spaces) equipped with the Gromov–Hausdorff metric.     

Smooth and palindromic Schubert varieties in affine Grassmannians

We completely determine the smooth and palindromic Schubert varieties in affine Grassmannians, in all Lie types. We show that an affine Schubert variety is smooth if and only if it is a closed parabolic orbit. In particular, there are only finitely many smooth affine Schubert varieties in a given Lie type. An affine Schubert variety is palindromic if and only if it is a closed parabolic orbit, a chain, one of an infinite family of “spiral” varieties in type A, or a certain 9-dimensional singular variety in type B ₃. In particular, except in type A there are only finitely many palindromic affine Schubert varieties in a fixed Lie type. Moreover, in types D and E an affine Schubert variety is smooth if and only if it is palindromic; in all other types there are singular palindromics. The proofs are for the most part combinatorial. The main tool is a variant of Mozes’ numbers game, which we use to analyze the Bruhat order on the coroot lattice. In the proof of the smoothness theorem we also use Chevalley’s cup product formula.     

Comparative study of the synthesis of layered transition metal molybdates

Mixed metal oxides (MMOs) prepared by the mild thermal decomposition of layered double hydroxides (LDHs) differ in their reactivity on exposure to aqueous molybdate containing solutions. In this study, we investigate the reactivity of some T-Al containing MMOs (T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates (LTMs) possessing the general formula AT₂(OH)(MoO₄)₂·H₂O, where A=NH₄⁺, Na⁺ or K⁺. The phase selectivity of the reaction was studied with respect to the source of molybdate, the ratio of T to Mo and the reaction pH. LTMs were obtained on reaction of Cu-Al and Zn-Al containing MMOs with aqueous solutions of ammonium heptamolybdate. Rehydration of these oxides in the presence of sodium or potassium molybdate yielded a rehydrated LDH phase as the only crystalline product. The LTM products obtained by the rehydration of MMO precursors were compared with LTMs prepared by direct precipitation from the metal salts in order to study the influence of preparative route on their chemical and physical properties. Differences were noted in the composition, morphology and thermal properties of the resulting products.     

High-pressure crystal growth and magnetic and electrical properties of the quasi-one dimensional osmium oxide Na2OsO4

Na₂OsO₄ crystals were grown by a NaCl flux method under high pressure. It crystallizes in the Ca₂IrO₄-type structure without having additional elements or metal vacancies, which are usually accommodated. It appears that Na₂OsO₄ is a metal-stoichiometric Ca₂IrO₄-type compound never been synthesized to date. Na₂OsO₄ has the octahedral environment of Os⁶⁺O₆ so that the electronic configuration is 5d², suggesting the magnetic S=1 ground state. However, magnetization, electrical resistivity, and specific heat measurements indicated that the non-magnetic S=0 state is much likely for Na₂OsO₄ than the S=1 state. Band structure calculations and the structure analysis found that the disagreement is probably due to the statically uniaxial compression of the OsO₆ octahedra, resulting in splitting of the t_2g band.     

The design of efficient and selective routes to a key 1,4-cis-substituted cyclohexylamide intermediate

This Letter describes the synthetic challenges in synthesising key 1,4-cis-substituted cyclohexylamide intermediate 1 for our research programme. Five different routes address the major issues of selectivity to afford the cis product in isomerically pure form and in high yield. Major purification issues were also encountered upon scaling some of the routes. The merits of the diverse routes are assessed and the reasoning given for which one was ultimately used for large-scale synthesis of 1.     

The glass transition and crystallization of ball milled cellulose

Samples of ball milled cellulose were prepared by ball milling pulps from eucalyptus and softwood (spruce/pine). Water sorption isotherms were obtained by both dynamic vapor sorption and equilibration over saturated salt solutions, in the water content range of 5–42% db (db = dry basis; water as a % age of total solids). Dynamic mechanical analysis using a pocket technique showed a water content dependent thermal transition occurring at the same temperature for the two pulp samples, which was interpreted as a glass transition. Fitting the data to a Couchman–Karasz relationship predicted a value for T _g of the dry cellulose of approximately 478 K, which was similar to values previously reported for other dry polysaccharides. No clear glass transition could be observed calorimetrically, although an endotherm at approximately 333 K was measured, which in polymers is normally attributed to enthalpic relaxation, however the lack of dependence of this endotherm on water content suggests that the melting of some weak associations, such as residual hydrogen bonds, could be a more credible explanation. An exotherm was also observed on heating, which was dependent on water content and which was attributed to partial crystallization of the cellulose. This was confirmed by Wide angle X-ray diffraction and cross polarization magic angle spinning ¹³C NMR (CPMAS NMR). The recrystallisation was predominantly to form I of cellulose. This was thought to be caused by a small amount of residual form I (probably less than 5%) acting as a template for the crystallizing material. Differential scanning calorimetry reheat curves showed the appearance of freezable water for water contents higher than 20%, as a result of a transfer of water to the amorphous phase following crystallization. The increase in cellulose rigidity following crystallization was also confirmed by CPMAS NMR relaxation. Low resolution proton NMR T ₂ relaxation suggested the presence of proton water/cellulose exchange, which was active at water contents of 20% and above.