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Clathrate Formation from Octaazaphthalocyanines Possessing Bulky Phenoxyl Substituents: A New Cubic Crystal Containing Solvent‐Filled, Nanoscale Voids
Author(s) -
Makhseed Saad,
Ibrahim Fadi,
Samuel Jacob,
Helliwell Madeleine,
Warren John E.,
Bezzu C. Grazia,
McKeown Neil B.
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200701980
Subject(s) - solvent , nanoporous , chemistry , crystallography , crystal (programming language) , single crystal , steric effects , materials science , organic chemistry , computer science , programming language
The synthesis of octaazaphthalocyanine (AzaPc) derivatives, with bulky phenoxyl substituents placed at eight peripheral positions and containing either H + , Ni 2+ or Zn 2+ ions in their central cavity, is described. The required precursors, derivatives of pyrazine‐2,3‐dicarbonitrile, were prepared using a nucleophilic aromatic substitution reaction between 2,6‐diisopropylphenol or 2,6‐diphenylphenol and 5,6‐dichloropyrazine‐2,3‐dicarbonitrile. Analysis of the resulting AzaPcs by UV/Visible and 1 H NMR spectroscopy confirms that steric isolation of the AzaPc cores was enforced both in solution and in the solid state. X‐ray diffraction studies of single crystals of the AzaPcs reveal that solvent inclusion takes place in each case. Of particular significance is the finding that the zinc derivative of 2,3,9,10,16,17,23,24‐octa‐(2,6‐diisopropylphenoxy)octaazaphthalocyanine provides nanoporous cubic crystals, containing massive (8 nm 3 ) solvent‐filled voids, similar to those of the analogous phthalocyanine derivative. Exchange of the included solvent within the voids can be readily achieved by using a number of alternative solvents including water. Based on the observed loading of included water, the internal volume of this nanoporous cubic crystal appears to be more hydrophilic than its phthalocyanine counterpart.