[R-C{sub 7}H{sub 16}N{sub 2}][V{sub 2}Te{sub 2}O{sub 10}] and [S-C{sub 7}H{sub 16}N{sub 2}][V{sub 2}Te{sub 2}O{sub 10}]; new polar templated vanadium tellurite enantiomers

Journal Article · Wed Jun 15 00:00:00 EDT 2011 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2011.04.016· OSTI ID:21580106

Glor, Ethan C; Blau, Samuel M ^[1]; Yeon, Jeongho ^[2]; Zeller, Matthias ^[3]; Shiv Halasyamani, P ^[2]; Schrier, Joshua ^[1]

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1. Department of Chemistry, Haverford College, PA 19041 (United States)
2. Department of Chemistry, University of Houston, Houston, TX 77204 (United States)
3. Department of Chemistry, Youngstown State University, Youngstown, OH 44555 (United States)

New polar vanadium tellurite enantiomers have been synthesized under mild hydrothermal conditions through the use of sodium metavanadate, sodium tellurite and enantiomerically pure sources of either R-3-aminioquinuclidine or S-3-aminioquinuclidine. [R-C{sub 7}H{sub 16}N{sub 2}][V{sub 2}Te{sub 2}O{sub 10}] and [S-C{sub 7}H{sub 16}N{sub 2}][V{sub 2}Te{sub 2}O{sub 10}] contain [V{sub 2}Te{sub 2}O{sub 10}]{sub n}{sup 2n-} layers constructed from [(VO{sub 2}){sub 2}O(TeO{sub 4}){sub 2}] monomers. Steric effects associated with the hydrogen-bonding network between the [V{sub 2}Te{sub 2}O{sub 10}]{sub n}{sup 2n-} layers and [C{sub 7}H{sub 16}N{sub 2}]{sup 2+} result in polar structures and crystallization in the space group P2{sub 1} (no. 4). Electron localization functions were calculated to visualize the tellurite stereoactive lone pairs. Both iterative and non-iterative Hirshfeld techniques were evaluated as means to determine atomic partial charges, with iterative Hirshfeld charges more accurately representing charge distributions in the reported enantiomers. These charges were used to calculate both component and net dipole moments. [R-C{sub 7}H{sub 16}N{sub 2}][V{sub 2}Te{sub 2}O{sub 10}] and [S-C{sub 7}H{sub 16}N{sub 2}][V{sub 2}Te{sub 2}O{sub 10}] exhibit dipole moments of 17.37 and 16.62D, respectively. [R-C{sub 7}H{sub 16}N{sub 2}][V{sub 2}Te{sub 2}O{sub 10}] and [S-C{sub 7}H{sub 16}N{sub 2}][V{sub 2}Te{sub 2}O{sub 10}] both display type 1 phase-matching capabilities and exhibit second harmonic generation activities of {approx}50x{alpha}-SiO{sub 2}. - Graphical abstract: Two new vanadium tellurite enantiomers have been synthesized under mild hydrothermal conditions. Hydrogen-bonding between [C{sub 7}H{sub 16}N{sub 2}]{sup 2+} cations and [V{sub 2}Te{sub 2}O{sub 10}]{sub n}{sup 2n-} layers results in polar structures that exhibit type 1 phase matching capabilities. Component and net dipole moments were calculated from atomic positions and iterative Hirshfeld partial charges. Highlights: > A pair of new polar templated vanadium tellurite enantiomers is reported. > Sterics in the hydrogen-bonding network drive the compound polarities. > Iterative Hirshfeld portioning was used to calculate atomic partial charges.{yields} Net and component dipole moments are calculated for each compound.{yields} Type 1 phase matching behavior and SHG activities of {approx}50x{alpha}-SiO{sub 2} are found.

• OSTI ID: 21580106
• Journal Information: Journal of Solid State Chemistry, Vol. 184, Issue 6; Other Information: DOI: 10.1016/j.jssc.2011.04.016; PII: S0022-4596(11)00184-8; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHARGE DISTRIBUTION
CRYSTALLIZATION
DIPOLE MOMENTS
HARMONIC GENERATION
HYDROGEN
ITERATIVE METHODS
LAYERS
MONOCLINIC LATTICES
SILICA
SILICON OXIDES
SODIUM
SPACE GROUPS
VANADATES
VANADIUM
VANADIUM OXIDES
ALKALI METALS
CALCULATION METHODS
CHALCOGENIDES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
ELEMENTS
FREQUENCY MIXING
METALS
MINERALS
NONMETALS
OXIDE MINERALS
OXIDES
OXYGEN COMPOUNDS
PHASE TRANSFORMATIONS
SILICON COMPOUNDS
SYMMETRY GROUPS
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
VANADIUM COMPOUNDS