The treatment of boron(III) subphthalocyanine chloride (SPcCl) with 3-or 4-hydroxypyridine in the presence of pyridine in toluene gave the corresponding boron(III) subphthalocyanine pyridinolates SPc(3-OPy) (1) or SPc(4-OPy) (2). Having a pyridyl group, these compounds could axially complex with a series of zinc(II) and ruthenium(II) porphyrins and phthalocyanines to form the corresponding subphthalocyanine-porphyrin and subphthalocyanine-phthalocyanine heterodyads. As revealed by UV-vis spectroscopy, the ground-state interaction between the two chromophores in these dyads is insignificant. The complexation processes were also studied by H-1 NMR and fluorescence spectroscopic methods, which confirmed the 1:1 binding stoichiometry. The association constants, as determined by fluorescence titration, were generally higher for the ruthenium(11) tetrapyrroles [(2.5-4.7) x 10(4) M-1] than for the zinc(II) counterparts [(0.3-1.8) x 10(4) M-1]. The molecular structures of the two pyridyl subphthalocyanines 1 and 2, together with three novel subphthalocyanine-porphyrin heterodyads, were also determined by X-ray diffraction analyses.