Highly emissive,nine-coordinate enantiopure lanthanide complexes incorporating tetraazatriphenylenes as probes for DNA

The interaction of q = 0 delta- and lambda-Tb and Eu complexes with poly(dAdT), poly(dGdC) and calf-thymus DNA has been examined by absorption, emission and chiroptical spectroscopy and is sensitive to complex helicity, base-pair type and the nature of the lanthanide excited state.     

Polyferrocenylsilane microspheres: synthesis,mechanism of formation,size and charge tunability,electrostatic self-assembly,and pyrolysis to spherical magnetic ceramic particles

Pt(0)-catalyzed ring-opening precipitation copolymerization of [1]silaferrocenophanes fcSiMe(2) (3) and the spirocyclic cross-linker fcSi(CH(2))(3) (4) (fc = Fe(eta(5)-C(5)H(4))(2)) was used to prepare polyferrocenylsilane microspheres (PFSMSs) under mild conditions. By varying the reaction conditions, a wide variety of other morphologies was obtained. The effects of temperature, monomer ratio, solvent composition, catalyst concentration, and time on the observed morphology were investigated and interpreted in terms of a mechanism for microsphere formation. The most well-defined particles were formed using equimolar amounts of 3 and 4, in a 50:50 mixture of xylenes and decane at 60 degrees C with gentle agitation. Chemical oxidation of the polymeric microspheres led to positively charged particles (OPFSMSs) which underwent electrostatically driven self-assembly with negatively charged silica microspheres to form core-corona composite particles. Redox titration with controlled amounts of the one-electron oxidant [N(C(6)H(4)Br-p)(3)][PF(6)] in acetonitrile led to the oxidation of the outer 0.15 microm (ca. 32%) of the PFSMSs. The resulting OPFSMSs were reduced back to their neutral form by reaction with hydrazine in methanol. Pyrolysis of the PFSMSs led to spherical magnetic ceramic replicas with tunable magnetic properties that organize into ordered 2-D arrays at the air-water interface under the influence of a magnetic field.     

Spin polarization of CrO2 at and across an artificial barrier

We report a systematic study of the spin polarization of epitaxial CrO2 films at and across an interface using planar junctions with a superconducting counterelectrode. By chemical modification of the CrO2 surface before the deposition of the superconductor, junctions with a wide range of barrier strength were obtained. Analysis of the conductance data on these junctions, especially under Zeeman splitting of the superconducting density of states, yields consistent, close to full spin polarization for CrO2 regardless of the barrier strength.     

The Vibrational Inelastic Neutron Scattering Spectrum of Dodecahedrane: Experiment and DFT Simulation

Vibrational frequencies that are forbidden in Raman and IR absorption can be observed by inelastic neutron scattering. In the case of the I(h)-symmetrical molecule dodecahedrane (shown schematically), the resulting spectrum agrees with a DFT calculation.     

Factors affecting coercivity in (Y,Sm,Tm)3(FeGa)5O12 and (Y,Sm,Lu,Ca)3(FeGe)5O12 LPE films

Factors which influence coercivity, H_c, in (Y,Sm,Lu,Ca)₃(FeGe)₅O₁₂ films and in (Y,Sm,Tm)₃(FeGa)₅O₁₂ films grown by LPE have been identified. An anomalous layer at the film-substrate interface exhibits coercivity values different from that of the middle, bulk, portion of the film. The contribution of the transient layer at the substrate interface could be reduced by increasing the rotation rate while immersing the substrate into the melt. Films containing Ga show lower coercivities than films containing CaGe possibly because films with Ga are more uniform in composition. Films with Ga show increased coercivities with increasing growth rates and with increasing Sm content throughout the film.     

Mononuclear anionic formyl complexes; synthesis and properties

A series of kinetically unstable mononuclear anionic formyl complexes have been prepared by the action of Li(C₂H₅)₃BH on neutral metal carbonyl precursors. One of these, Li⁺[(CO)₄Mn(COC₆H₅)(CHO)]^?, is shown to decompose by a hydride transfer disproportionation mechanism involving the by-product (C₂H₅)₃B.     

Determination of optical purity at isotopically chiral sites by 2H NMR

Techniques have been developed which permit the direct analysis of optical purity in α-deuterated amines and carboxylic acids.