The article reviews the exploitation of the serendipitous discovery that dihydroxysilicon 1,4,8,11,15,18,22,25-octakis(hexyl)phthalocyanine 1 reacts at one face only to form a µ-oxo linked bond to dichlorosilicon phthalocyanine. Reaction of 1 with dihydroxysilicon octaethylporphyrin led to an unstable µ-oxo linked Pc-O-Pn heteroligand dyad that could not be isolated. However, reaction with dihydroxygermanium octaethylporphyrin gave a stable dyad that showed substantial broad band absorption attributable to exciton effects. A small amount of the µ-oxo linked homo dyad formed by self-condensation of dihydroxygermanium octaethylporphyrin was detected by MALDI-TOF mass spectrometry but was not isolated. Reaction of 1 with chloroboron subphthalocyanine afforded the stable Pc-O-SubPc heterodyad as the main product and the SubPc-O-Pc-O-SubPc triad as a minor side product. Both gave absorption spectra that showed the main features of the ligands present, implying limited exciton coupling. A further reaction of 1 with axial-hydroxy, axial-methyl silicon phthalocyanine provided a key Pc-O-Pc' dyad that proved to be an ideal intermediate for developing a synthetic strategy to access a series of hetero-metalloid/hetero-ligand Pc-O-Pc'-O-Pn triads. X-ray structural data for examples of these arrays are discussed. A feature of the triad compounds is their very broad band absorption spectra that extends from the UV through the visible region to near IR wavelengths.