A straightforward and generalizable synthesis of metal-free and metal (Cu, Co, Ni, or Fe) derivatives of a symmetrically tetrasubstituted phthalocyanine derived from 15,16-dicyano-2,3,5,6,8,9,11,12-octahydro-benzo[1,4,7,10,13]pentaoxacyclopentadecine is described. The new compounds have been characterized by elemental analyses, and i.r., ¹H n.m.r., u.v.–visible, and fast atom bombardment mass spectra. The alkali metal ions (sodium and potassium) bound to crown ether groups of the metal complexes force dimerization of the phthalocyanine units in solution as observed in the electronic spectra by the broadening of the Q-band transition at ca. 630 nm. The solubilities of the metal phthalocyaninates in chloroform were determined to be ca. 10^–3 mol dm^–3. The thermal stabilities of the compounds were determined by thermogravimetric and differential thermal analysis. The high affinity of the cobalt(II) derivative for the potassium ion was observed in solvent extraction experiments.