Various synthetic strategies have been developed to devise a variety of covalently linked porphyrin arrays as molecular photonic devices because of their similarities in architecture and subunit structures to the natural photosynthetic light-harvesting complexes. Such research involves the exploitation of a wide range of linkage motifs such as butadiyne, ethene, ethyne, naphthalene, p-phenylene, as well as carbon-carbon single bond directly linking the constituent porphyrins. Although influences of the linkages on the ground and excited state electronic couplings and concomitant photophysical properties, such as excitation energy transfer processes, have extensively been investigated by ultrafast spectroscopic techniques, systematic approaches on this issue at the single-molecule level have not yet been performed despites its great importance in gratifying the relentless demand on the realization of device miniaturization.
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