Porphyrins Linked Directly to the 5,5‘ Positions of 2,2‘-Bipyridine:  A New Supramolecular Building Block and Switch

The synthesis and coordination chemistry of two porphyrin dimers linked either at the 5,5‘ or the 4,4‘ positions of 2,2‘-bipyridine are described. These compounds, which may serve a molecular tectons for the constructions of a variety of supramolecular arrays of diverse function, reveal that the ground- and excited-state electronic communication between the chromophores is only moderately affected by the complexation state of the bipyridyl moiety. The nature of the metal ion chelated by the bipyridine only slightly perturbs the ground-state spectra, and differences observed in the excited state are largely ascribed to the heavy atom effect. This work also shows that conformational changes in structural subunits, in this case induced by bipyridyl complexation of various metal ions, do not necessarily require reorganization of supramolecular systems.