Controlling Electron Delocalization in Vanadium-Based Hybrid Bronzes through Molecular Templation.

We show that the conductivity of hybrid vanadium bronzes-mixed-valence organic-inorganic vanadium oxides-can be tuned over six orders of magnitude through judicious choice of molecular component. By systematically varying the steric profile, charge density, and propensity to hydrogen bond across a series of eight diammonium-based molecules, we engender multiple distinct motifs of V-O connectivity within the two-dimensional vanadium oxide layers of a family of bulk crystalline hybrid materials. A combination of single-crystal and powder X-ray diffraction analysis, variable-temperature electrical transport measurements, and a range of spectroscopic methods, including UV/Visible diffuse reflectance, X-ray photoelectron, and electron paramagnetic resonance are employed to probe how vanadium oxide layer topology correlates with electron localization. Specifically, alkylammonium molecules yield hybrids featuring more corrugated layers that contain V-O tetrahedra as well as a higher ratio of corner-sharing to edge-sharing polyhedra and that exhibit highly localized electronic behavior, while alkyl bipyridinium molecules yield more regular layers with polyhedral edge-sharing that show substantially delocalized electronic behavior. This work allows for the development of design principles based on structure-property relationships and brings the charge transport capabilities of hybrid vanadium bronzes to more technologically relevant levels.

Rare earth arylsilazido compounds with inequivalent secondary interactions.

A new bulky silazido ligand, -N(SiHMe2)Dipp (Dipp = C6H3-2,6-iPr2), supports planar, three-coordinate homoleptic rare earth complexes Ln{N(SiHMe2)Dipp}3 (Ln = Sc, Y, and Lu), each containing three secondary Ln↼HSi interactions and one agostic CH bond. Y{N(SiHMe2)Dipp}3 and acetophenone react via hydrosilylation, rather than by insertion into the Y-N bond or by enolate formation.