Möbius Aromatic [28]Hexaphyrin Germanium(IV) and Tin(IV) Complexes: Efficient Formation of Triplet Excited States

28]Hexaphyrin Ge^IV and Sn^IV complexes were synthesized in high yields by reactions of 28]hexaphyrin with GeCl₄ or SnCl₄ in the presence of triethylamine. Both complexes display distinct 28π Möbius aromatic character and possess a trigonal bipyramidal geometry at the central Ge^IV or Sn^IV atom. The equatorial hydroxy group of the Ge^IV complex was smoothly exchanged with neutral nucleophiles, such as phenol derivatives and thiophenol, with retention of configuration. In the Sn^IV complex, intersystem crossing to the T₁ state is remarkably enhanced owing to the effective heavy‐atom effect, thus allowing the formation of the T₁ state in high yield. The T₁ states of the Ge^IV and Sn^VI complexes were found to be antiaromatic on the basis of the transient absorption features in line with the Baird rule.