Vanadium Selenite Frameworks

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Title: Vanadium Selenite Frameworks
Author: Olshansky, Jacob H.
Advisor: Norquist, Alexander J.
Department: Haverford College. Dept. of Physics
Type: Thesis (B.S.)
Issue Date: 2012
Abstract: Organically templated vanadium selenites are of particular interest owing to their potential to exhibit the technologically applicable properties of microporosity and noncentrosymmetry. To date, only eight amine templated vanadium selenites have been reported. Fifteen novel vanadium selenite compounds were hydrothermally synthesized and characterized using single crystal X-ray diffraction in the current study. A 1,4-dimethylpiperazinium cation resulted in a structure containing inorganic chains with a [VO(SeO3)(HSeO3)]n 2n- formula (1). However, using 2,5-dimethylpiperazine (3), 2-methylpiperazine (4), diethylenetriamine (5), and N,N’-dimethylethylenediamine (6) resulted in framework structures containing the same chain moiety as seen in compound 1. The charge per length of these amines was found to affect the vanadium oxidation states in the framework. A distinct polar framework with a [(VO)3(SeO3)2(HSeO3)4]n 2n- inorganic structure was templated by 2-methylpiperazine. Both racemic (7) and (S)-2-methylpiperazine (8) were used as templates. The component and net dipole moments in 8 were calculated using density functional theory and Iterative Hirshfeld partial atomic charges. The chiral amines, 3-aminoquinuclidine (10) and 3-aminopyrrolidine (11), yielded centrosymmetric structures with analogous layer topologies composed of [V3O5(SeO3)3]n 2n-. The introduction of oxalate into this chemistry resulted in three novel compounds containing [(VO)2(C2O4)(SeO3)2]n 2n- layers templated by 1-methylpiperazine (12), 2- methylpiperazine (13), or 2,5-dimethylpiperazine (14).
Subject: Selenites
Subject: Vanadium
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Olshansky, Jacob H.. "Vanadium Selenite Frameworks". 2012. Available electronically from

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