Head‐to‐tail self‐assembly of two imidazolylphthalocyaninatozinc(II) or ‐magnesium(II) units through mutual imidazole–metal interactions leads to strongly fluorescent dimers (see picture, ΦF=fluorescence quantum yield) that exhibit high association constants estimated at over 1011 M−1 in toluene.

Organized multiporphyrin arrays were developed on the conductive surface by a novel coordination-directed molecular architecture aiming at efficient photoelectric conversion. The basic strategy employs the mutual coordination of two imidazolylporphyrinatozinc(II) units to form a cofacial dimer. Thus, meso,meso-linked bis(imidazolylporphyrinatozinc) (Zn2(ImP)2) was organized onto imidazolylporphyrinatozinc on the gold substrate as a self-assembled monolayer. The organized Zn2(ImP)2 bearing allyl side chains was covalently linked by ring-closing olefin metathesis catalyzed with Grubbs catalyst. Alternating coordination/metathesis reactions allow the stepwise accumulation of multiporphyrin arrays on the gold electrode. A successive increase in absorption over a wide wavelength range occurred after each accumulation step of Zn2(ImP)2 on the gold electrode, and cathodic photocurrent generation was enhanced in the aqueous electrolyte system, containing viologen as an electron carrier. The significant increase of the photocurrent indicates that the multiporphyrin array works as a "light-harvesting antenna" on the gold electrode.

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Oligomeric porphyrin arrays with an alternating pyridyl–porphyrin sequence were synthesized to explore double-strand formation through self-complementary pyridyl-to-zinc axial coordination bonds.

Imidazolyl-appended phthalocyaninatozinc(II) containing an ethynylporphyrin linkage was stacked by complementary coordination into an antiparallel dimer that displayed strong nonlinear optical properties involving two-photon and three-photon absorptions.