Cu(I)-mediated alkoxylation of doubly 1,3-butadiyne-bridged carbazole dimer 1, followed by acid-catalyzed cyclization, provided furan-bridged carbazole dimer 3, while annulation reaction of 1 with selenium in the presence of hydrazine monohydrate provided selenophene-bridged carbazole dimer 5a. Oxidation of isophlorin 5a afforded carbazole-based selenaporphyrin 5b, which possessed distinct aromaticity and produced intensified and red-shifted absorption bands in the near-IR region.

It has been demonstrated that the direction and magnitude of transition dipole moments, and hence rates in the excitation energy hopping in the self-assembled porphyrin boxes can be tuned by insertion of ethynyl groups as well as the dielectric constant of solvent.

The carbazole- and indolone-based porphyrinoids 3 and 4 were synthesized by stepwise transition-metal-catalyzed coupling reactions. Palladium metalation of 4 produced 4Pd, which exhibits near-infrared absorption.

Peripherally ethynylated carbazole-based core-modified porphyrins were synthesized by sequential metal-catalyzed coupling and annulation reactions. Experimental results and DFT calculations both confirm that the π-conjugated networks of the resulting porphyrins effectively delocalize over the entire macrocycle, including the ethynyl substituent groups.

Peripherally ethynylated carbazole-based core-modified porphyrins were synthesized by sequential metal-catalyzed coupling and annulation reactions. Experimental results and DFT calculations both confirm that the π-conjugated networks of the resulting porphyrins effectively delocalize over the entire macrocycle, including the ethynyl substituent groups.

It has been demonstrated that the direction and magnitude of transition dipole moments, and hence rates in the excitation energy hopping in the self-assembled porphyrin boxes can be tuned by insertion of ethynyl groups as well as the dielectric constant of solvent.