4.7 Article

Formation Principles for Vanadium Selenites: The Role of pH on Product Composition

期刊

INORGANIC CHEMISTRY
卷 53, 期 22, 页码 12027-12035

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AMER CHEMICAL SOC
DOI: 10.1021/ic501736r

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资金

  1. NSF [DMR-1307801, 0087210]
  2. Henry Dreyfus Teacher-Scholar Awards Program
  3. HHMI Undergraduate Science Education Program
  4. Ohio Board of Regents Grant [CAP-491]
  5. Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
  6. Division Of Materials Research
  7. Direct For Mathematical & Physical Scien [1307801] Funding Source: National Science Foundation

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A series of organically templated vanadium selenites has been prepared under mild hydrothermal conditions. Single crystals of [C5H14N2][(VO)(3)(SeO3)(2)(HSeO3)(4)], [C5H14N2][VO(SeO3)(2)], [(R)-C5H14N2][(VO)(3)(SeO3)(2)(HSeO3)(4)], and [(S)-C5H14N2][(VO)(3)(SeO3)(2)(HSeO3)(4)] were grown from VOSO4, SeO2, and 2-methylpiperazine. Controlling the initial pH of the reaction mixture allows for one to select between the compounds found in the VOSO4/SeO2/(2)-methylpiperazine system, as the solution pH directly affects the relative ratio of the HSeO3- and SeO32- concentrations. Moreover, partial resolution of racemic 2-methylpiperazine is observed in [C5H14N2][(VO)(3)(SeO3)(2)(HSeO3)(4)], which is understood through the use of a one-dimensional Ising model. The use of enantiomerically pure 2-methylpiperazine results in fully ordered and fully resolved structures.

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