The reaction of p-benziporphyrin, sodium tetrachloroaurate(III) dihydrate, and potassium carbonate in dichloromethane yielded gold(III) 5,10,15,20-tetraaryl-21-carbaporphyrin owing to the contraction of p-phenylene to cyclopentadiene. This molecule is the very first representative of a true 5,10,15,20-tetraaryl-21-carbaporphyrin complex where four trigonal donor atoms are involved in equatorial coordination. The contraction adds an unprecedented route to numerous organic transformations of aromatic compounds catalyzed by simple gold(III) compounds. p-Benziporphyrin provided the unique environment to alter the fundamental reactivity of the benzene unit facilitating its contraction to cyclopentadiene.

32-Hetero-5,6-dimethoxyphenanthrisapphyrins-macrocycles that link structural features of polycylic aromatic hydrocarbons and expanded porphyrins-were obtained in a straightforward [3+1] condensation reaction of dimethoxyphenanthritripyrrane and 2,5-bis(arylhydroxymethyl)heterocyclopentadienes. The highly folded conformation of formally 4 n π-electron macrocycles causes them to manifest only limited macrocyclic π conjugation as explored by means of NMR spectroscopic and X-ray structural analyses, and supported by DFT calculations. Although protonation does not change their π-conjugation characteristics, the cleavage of ether groups at the phenanthrenylene moiety yields nonaromatic 32-hetero-5,6-dioxophenanthrisapphyrins.

Antiaromatic phenanthriporphyrin and nonaromatic 5,6-dioxophenanthriporphyrin reveal specific reactivity toward protic and Lewis acids yielding respectively nonaromatic and aromatic macrocycles.

The analogue of octaphyrin(1.1.1.0.1.1.1.0) bearing two dimethoxyphenanthrene units was synthesized and characterized in solution and solid state. The macrocycle was demonstrated to exist as two locked conformers that can be easily separated and handled individually. The conversion of conformers was proven to be facilitated by the presence of hydrogen-bond acceptors, such as amines. The bis-boron(III) complex of diphenanthrioctaphyrin has been obtained, proving that the metalloid center acts as the topology selector stabilizing only one conformation of the macrocycle, irrespective of the stereoisomer used for the insertion. Both conformers of diphenanthrioctaphyrin, as well as the boron complex formed from them, have been separated into enantiomers using HPLC with a chiral stationary phase. All of these systems have shown strikingly different stereodynamic behavior.

phyrin 2 act as suitable organometallic ligands for copper(III), adopting trianionic [CCNN] coordination cores. Under oxidizing conditions, in the presence of methanol, copper(III) phenanthriporphyrin 1-Cu undergoes transformation to copper(III) phenanthriporphodimethene with methoxy substituents attached to two trans meso positions. Addition of acids to 1-Cu yields two isomeric copper(III) isophenanthriporphyrins protonated on one of the meso carbon atoms. Protonation of copper(III) 5,6-dioxophenanthriporphyrin 2-Cu yields the aromatic diprotonated complex 2-Cu-H 2 2+ . In the presence of HBF 4 2-Cu undergoes borylation at the carbonyl oxygen atoms, forming an aromatic exocyclic boron(III) complex.