A new host for polymer and small-molecule clathration

Harry R. Allcock, Nicolas J. Sunderland, A. Paul Primrose, Arnold L. Rheingold, Ilia A. Guzei, Masood Parvez

Research output: Contribution to journalArticle

25 Scopus citations

Abstract

The synthesis and inclusion properties of a new clathration host, tris(3,6-dimethylphenylenedioxy)cyclotriphosphazene, is described. The guest-free structure has a triclinic unit cell, space group P1̄, with unit cell dimensions a = 9.418(1) Å, b = 17.887(4) Å, c = 8.036(2) Å, α = 95.50(2)°, β = 100.57(1)°, and γ = 95.58(1)°. Recrystallization of the host from dioxane or from a poly(tetramethylene oxide)/benzene mixture afforded two different guest-included structures. The tris(3,6-dimethylphenylenedioxy)cyclotriphosphazene-dioxane inclusion adduct crystallizes in a monoclinic system, space group P21/c, with unit cell dimensions a = 9.3481(1), b = 19.6569(1), c = 16.4099(3), and β = 97.351(1)°. The guest occupies a cagelike void located between the phosphazene rings. The poly(tetramethylene oxide) adduct crystallizes in a hexagonal system, space group P63/m, with unit cell dimensions a = 11.4902(2) Å and c = 13.3138(3) Å. In this case, the polymeric guest is located in tunnels created along the c-axis. Adduct formation also occurs between tris(3,6-dimethylphenylenedioxy)cyclotriphosphazene and other cyclic, linear, and polymeric species such as tetrahydrofuran, methylene chloride, polyethylene, and cis-polybutadiene. Thermogravimetric analysis and differential scanning calorimetry were used to characterize the thermal behavior of the inclusion adducts. Crystal engineering of these spirocyclotriphosphazene hosts is facilitated by the ease in which the void and tunnel diameter can be tailored by systematic adjustments to the size and nature of the side group.

Original languageEnglish (US)
Pages (from-to)2478-2485
Number of pages8
JournalChemistry of Materials
Volume11
Issue number9
DOIs
StatePublished - Jan 1 1999

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Fingerprint Dive into the research topics of 'A new host for polymer and small-molecule clathration'. Together they form a unique fingerprint.

  • Cite this

    Allcock, H. R., Sunderland, N. J., Primrose, A. P., Rheingold, A. L., Guzei, I. A., & Parvez, M. (1999). A new host for polymer and small-molecule clathration. Chemistry of Materials, 11(9), 2478-2485. https://doi.org/10.1021/cm990291e