Abstract
A comprehensive study of supramolecular polymerization of ditopic zinc (2-pyridylethynyl)porphyrin dimer 1 in toluene and thin films was performed. A glass-forming porphyrin bearing 3,4,5-tri((S)-3,7-dimethyloctyloxy)phenyl groups, named “porphyrin glass”, was introduced with the 2-pyridylethynyl group as a supramolecular organizing unit; two zinc (2-pyridylethynyl)porphyrins were held together by self-complementary pyridyl-to-zinc coordination bonds to form a slipped-cofacial stack. Then, ditopic zinc (2-pyridylethynyl)porphyrin could be extended to a linear supramolecular polymer. The small binding constant limited the degree of supramolecular polymerization of 1 in toluene solution. In spin-cast film, on the other hand, 1 adopted a form of supramolecular polymer of porphyrin glass, which was effective enough to display a large bathochromic shift of the absorption bands exceeding the narrowest limit of the optical band gap extrapolated from the electronic structures in solution. The supramolecularly pol...
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