Discrete Giant Porphyrin Arrays: Challenges to Molecular Size, Length and the Extent of Electronic π-Conjugation

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Abstract
Our studies on synthesis of directly meso-meso-linked and fused porphyrin arrays were reviewed. AgI-promoted meso-meso coupling reaction of 5,15-diaryl ZnII-porphyrins is advantageous in light of its high regioselectivity as well as its easy extension to large porphyrin arrays. Doubling reactions have been repeated to make 128-mer as the longest man-made discrete molecule. The similar coupling reaction has been applied to 1,4-phenylene-bridged linear porphyrin arrays, providing three dimensionally arranged windmill porphyrin arrays and grid-like porphyrin arrays. meso-β Doubly-linked diporphyrins were prepared by oxidations of 5,15-diaryl CuII-, NiII-, and PdII-porphyrins with (p-BrC6H4)3NSbCl6 (BAHA). In a similar manner, meso,meso-end capped meso-meso linked CuII-, NiII-, and PdII-diporphyrins were converted into meso-meso β-β, β-β triply-linked fused diporphyrins. We developed an alternative, more effective method to convert meso-meso-linked diporphyrins to triply-linked diporphyrins by using DDQ as an oxidant in the presence of ScIII-salt, which, when applied to higher meso-end capped meso-meso linked ZnII-porphyrin arrays, allowed the synthesis of fully conjugated triply-linked ZnII-porphyrin arrays up to 12-mer which exhibited a low-energy electron absorption band reaching the infrared region.

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