Stable meso-Aryl β-Alkyl Hybrid Sapphyrin with a Warped π-Conjugation Circuit and Neo-Confused Sapphyrin-Silver(I) Complex.

A meso-aryl and β-alkyl substituted sapphyrin and its rhodium(I) and silver complexes were synthesized. This sapphyrin was so stable that the non-inverted and warped structure could be analyzed by X-ray crystallography even in its neutral state. Its bis-rhodium(I) complex has a more planar structure than the sapphyrin with enhanced aromaticity over the conjugation circuit. On the other hand, silver metalation of the sapphyrin caused a marked core rearrangement into a neo-confused sapphyrin derivative with a C(α)-N bond and a twisted macrocycle.