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

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

Research output: Contribution to journalArticle

  • 5 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
Hexanes
Hexane
Solubility
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: Contribution to journalArticle

@article{b0215d02d0384ca593dd69627cbc5f91,
title = "Separation and solubility of cis and trans isomers in nanostructured double-decker silsequioxanes",
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 Schr{\"o}der-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 (Schr{\"o}der-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.",
author = "Schoen, {Beth W.} and Lira, {Carl T.} and Andre Lee",
year = "2014",
month = "5",
day = "8",
doi = "10.1021/je4010245",
language = "English (US)",
volume = "59",
pages = "1483--1493",
journal = "Journal of Chemical & Engineering Data",
issn = "0021-9568",
publisher = "American Chemical Society",
number = "5",

}

TY - JOUR

T1 - Separation and solubility of cis and trans isomers in nanostructured double-decker silsequioxanes

AU - Schoen,Beth W.

AU - Lira,Carl T.

AU - Lee,Andre

PY - 2014/5/8

Y1 - 2014/5/8

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84900346083&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84900346083&partnerID=8YFLogxK

U2 - 10.1021/je4010245

DO - 10.1021/je4010245

M3 - Article

VL - 59

SP - 1483

EP - 1493

JO - Journal of Chemical & Engineering Data

T2 - Journal of Chemical & Engineering Data

JF - Journal of Chemical & Engineering Data

SN - 0021-9568

IS - 5

ER -