The Role of Stereoactive Lone Pairs in Templated Vanadium Tellurite Charge Density Matching

The role of charge density matching was investigated in the formation of templated vanadium tellurites under mild hydrothermal conditions. Reactions were conducted using a fixed NaVTeO5:amine ratio in an ethanol/water solution to isolate the effects of amine structure. The use of 1,4-diaminobutane, 1,3-diaminopropane, and piperazine resulted in three distinct vanadium tellurite connectivities, [V2Te2O10](n)(2n-) chains, [V2TeO8](n)(2n-) layers, and [V2Te2O10](n)(2n-) layers, respectively. Charge density matching with the protonated amines is the primary influence over the structure of each vanadium tellurite anion, as quantified by molecular surface area and geometric decomposition methods. Electron localization functions were calculated using the Stuttgart tight-binding linear muffin-tin orbital, atomic sphere approximation code, to visualize the location and relative size, shape, and orientation of the stereoactive lone pair in the tellurite groups. [C4H14N2][V2Te2O10]: a = 5.649(5) angstrom, b = 6.348(5) angstrom, c = 9.661(5) angstrom, alpha = 84.860(5)degrees, beta = 85.380(5)degrees, gamma=81.285(5)degrees, triclinic, P (1) over bar (No. 2), Z=1. --author-supplied descriptio

Beyond Charge Density Matching: The Role of C–H···O Interactions in the Formation of Templated Vanadium Tellurites

A hierarchy of influences in the formation of templated vanadium tellurites is described and discussed in the context of two new compounds. Three Haverford undergraduates appears as co-authors. --author-supplied description

Inducing polarity in [VO3]nn- chain compounds using asymmetric hydrogen-bonding networks

One centrosymmetric and a pair of polar noncentrosymmetric templated metavanadates were synthesized under mild hydrothermal conditions. Asymmetry in the hydrogen-bonding between either [(R)-C5H14N2]2+ or [(S)-C5H14N2]2+ and [VO3]nn- chains results in polar structures that exhibit type 1 phase-matching capabilities. Hirshfeld surfaces were used to probe the hydrogen-bonding networks and component and net dipole moments were calculated from atomic positions and iterative-Hirshfeld partial charges. --author-supplied descriptio