Effect of β-Substitution and β,β'-Fusion on the Formation of Boron Complexes of Porphycenes.

Boron(III) complexation was investigated in a series of β-substituted porphycenes. Unlike -arylporphycenes, these macrocycles undergo a facile complexation reaction. Upon fusion of the β,β'-positions of the porphycene ligand, the complexation resulted in fast insertion of boron, forming the -BOF complex.

Monothia [22]pentaphyrin(2.0.1.1.0): a core-modified isomer of sapphyrin.

A novel 22π-aromatic sapphyrin isomer endowed with an acene moiety was designed and realised for the first time as a core-modified monothia analogue. This macrocycle exhibited absorption and emission in the near-infrared region. It was diprotonated under strongly acidic conditions and bound to anions like sapphyrin.

In-Core N4-Coordination of Palladium(II) in Dinaphthoporphycene: Synthesis, Structure, and Photophysical Studies.

Dinaphthoporphycene (DNP) has emerged as a versatile ligand undergoing large out-of-plane distortion to form a cis-bimetallic complex with Pd(II) using Pd(OAc) and out-of-plane monometallic complexes with Pd(acac) and PtCl(PhCN). Herein, we are finally able to synthesize the in-core complex with Pd(II) using PdCl(PhCN) or PdCl. The crystal structure shows the palladium ion resides slightly above the N4-core, with the Pd(II) dimensionally dissenting with the typical square planarity displayed by the reported in-core DNP complexes with Ni(II) and Cu(II) ions.

3,6,13,16-Tetrapropylporphycene: Rational Synthesis, Complexation, and Halogenation.

We have designed and synthesized 3,6,13,16-tetrapropylporphycene for the first time as its alkyl analogue from ethyl 4-propyl-1-pyrrole-2-carboxylate. The substituent effect was found to be more intense than reported positional isomeric tetrapropylporphycenes. The freebase porphycene exhibited moderate fluorescence and complexation ability with divalent metal ions, including Zn(II), which displayed an enhanced emission quantum yield (∼30%).