Role of Hydrogen-Bonding in the Formation of Polar Achiral and Nonpolar Chiral Vanadium Selenite Frameworks

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• 作者：Jacob H. Olshansky ; Thanh Thao Tran ; Kristen J. Hernandez ; Matthias Zeller ; P. Shiv Halasyamani ; Joshua Schrier ; Alexander J. Norquist
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：October 15, 2012
• 年：2012
• 卷：51
• 期：20
• 页码：11040-11048
• 全文大小：515K
• 年卷期：v.51,no.20(October 15, 2012)
• ISSN：1520-510X

文摘

A series of organically templated vanadium selenites have been prepared under mild hydrothermal conditions. Single crystals were grown from mixtures of VOSO₄, SeO₂, and either 1,4-dimethylpiperazine, 2,5-dimethylpiperazine, or 2-methylpiperazine in H₂O. Each compound contains one-dimensional [VO(SeO₃)(HSeO₃)]_n^n- secondary building units, which connect to form three-dimensional frameworks in the presence of 2,5-dimethylpiperazine or 2-methylpiperazine. Differences in composition and both intra-secondary building unit and organic鈥搃norganic hydrogen-bonding between compounds dictate the dimensionality of the resulting inorganic structures. [1,4-dimethylpiperazineH₂][VO(SeO₃)(HSeO₃)]₂ contains one-dimensional [VO(SeO₃)(HSeO₃)]_n^n- chains, while [2,5-dimethylpiperazineH₂][VO(SeO₃)(HSeO₃)]₂路2H₂O contains a three-dimensional [VO(SeO₃)(HSeO₃)]_n^n- framework. The use of racemic 2-methylpiperazine also results in a compound containing a three-dimensional [VO(SeO₃)(HSeO₃)]_n^n- framework, crystallizing in the noncentrosymmetric polar, achiral space group Pca2₁ (no. 29), while analogous reactions containing either (R)-2-methylpiperazine or (S)-2-methylpiperazine result in noncentrosymmetric, nonpolar chiral frameworks that crystallize in P2₁2₁2 (no. 18). The formation of these noncentrosymmetric framework materials is dictated by the structure, symmetry, and hydrogen-bonding properties of the [2-methylpiperazineH₂]²⁺ cations.