Separation and solubility of cis and trans isomers in nanostructured double-decker silsequioxanes

Beth W. Schoen, Carl T. Lira, Andre Lee

    Research output: Research - peer-reviewArticle

    • 3 Citations

    Abstract

    A fractional crystallization method was used to separate the cis and trans isomers of three double-decker silsesquioxanes (DDSQs) with an aminophenyl moiety in a THF + hexanes solvent mixture. The experimental solubilities were fitted to the Schröder-van Laar equation with activity coefficients determined using the NRTL model by adjusting the binary interaction parameters. The ability to separate these cis and trans isomers was affected by the regioisomer (m- or p-aminophenyl) and the R moiety (cyclohexyl or methyl) coupled via silicon. For a given DDSQ compound, the variances between the solubilities of the cis and trans isomers depend on differences in thermal properties (Schröder-van Laar). Cis isomers were 33 times more soluble than trans isomers for p-aminophenyl (R = methyl) and 22 times more soluble for the analogous m-aminophenyl in a solution of THF and hexanes. For a more sterically hindered m-aminophenyl (R = cyclohexyl), the cis isomers were only 3.5 times more soluble, and the overall solubility was also the lowest. The magnitude of the binary interaction between DDSQ and nonsolvent (hexanes) was used to explain how quickly the solubility decreased as hexanes were added. The solubilities of the two m-aminophenyl structures decreased at similar rates, while the solubility of the p-aminophenyl structure decreased at a much lower rate since the magnitude of the binary interaction between p-aminophenyl and hexanes is smaller.

    LanguageEnglish (US)
    Pages1483-1493
    Number of pages11
    JournalJournal of Chemical and Engineering Data
    Volume59
    Issue number5
    DOIs
    StatePublished - May 8 2014

    Profile

    Isomers
    Solubility
    Hexanes
    Hexane
    Activity coefficients
    Silicon
    Crystallization
    Thermodynamic properties

    ASJC Scopus subject areas

    • Chemistry(all)
    • Chemical Engineering(all)

    Cite this

    Separation and solubility of cis and trans isomers in nanostructured double-decker silsequioxanes. / Schoen, Beth W.; Lira, Carl T.; Lee, Andre.

    In: Journal of Chemical and Engineering Data, Vol. 59, No. 5, 08.05.2014, p. 1483-1493.

    Research output: Research - peer-reviewArticle

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