Substituent effects on the volatility of metal β-diketonates

Bradley D. Fahlman, Andrew R. Barron

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91 Scopus citations

Abstract

Volatile trends are established for a series of M(β-diketonate)n complexes, where M = Cu (n = 2); Al, Sc, Cr, Fe, Co, Ga (n = 3); Zr (n = 4) and β-diketonate = acetylacetonate (acac), trifluoroacetylacetonate (tfac), hexafluoroacetylacetonate (hfac) and 2,2,6,6-tetramethyl-3,5-heptanedionate (tmhd). Sublimation enthalpies (ΔHsub) were calculated from thermogravimetric analysis (TGA) data, which show that the dependence of ΔHsub on the number and type of intermolecular Interactions appears to be more substantial than molecular mass effects. Irrespective of the metal, the ΔHsub values for the M(tmhd)3 derivative have a ΔHsub value of between 93 and 99% of that of the M(acac)3 derivative. In contrast, the M(tfac)3 and M(hfac)3 derivatives have ΔHsub values of ca. 82% and 54% of the values for the corresponding M(acac)3. Similar trends are observed for M(β-diketonate)2 and M(β-diketonate)4 derivatives. The relationship between the ΔHsub and (Tsub) of the substituted β-diketonate derivatives as compared with the values for parent M(acac)n may be used to predict either quantity for a range of M(β-diketonate)n complexes where the values for M(acac)n are known. Using the TGA sublimation data, vapour pressures have been calculated for each of the M(β-diketonate)n complexes.

Original languageEnglish
Pages (from-to)223-232
Number of pages10
JournalAdvanced Functional Materials
Volume10
Issue number3-5
StatePublished - 2000

Keywords

  • CVD precursor
  • Enthalpy of sublimation
  • Thermogravimetric analysis
  • Vapour pressure
  • β-diketonate

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