title: Hückel and Möbius expanded para-benziporphyrins: synthesis and aromaticity switching.
abstract: The four expanded p-benziporphyrins A,C-di-p-benzi[24]pentaphyrin(1.1.1.1.1), N-fused A-p-benzi[24]pentaphyrin, A,D-di-p-benzi[28]hexaphyrin(1.1.1.1.1.1), and A,C-di-p-benzi[28]hexaphyrin(1.1.1.1.1.1) were obtained in three-component Lindsey-type macrocyclizations. These compounds were explored as macrocyclic ligands and as potential aromaticity switches. A BODIPY-like difluoroboron complex was obtained from the A,C-di-p-benzi[24]pentaphyrin, whereas A,C-di-p-benzi[28]hexaphyrin yielded a Möbius-aromatic Pd(II) complex containing fused pyrrole and phenylene subunits. Conformational behavior, tautomerism, and acid-base chemistry of the new macrocycles were characterized by means of NMR spectroscopy and DFT calculations. Free base N-fused A-p-benzi[24]pentaphyrin showed temperature-dependent Hückel-Möbius aromaticity switching, whereas the A,C-di-p-benzi[28]hexaphyrin formed a Möbius-aromatic dication.
authors.affiliation: Department of Chemistry, University of Wrocław, 14 F. Joliot-Curie St., 50-383 Wrocław (Poland), Fax: (+48) 71-328-23-48.
authors.forename: Bartosz
authors.initials: B
authors.lastname: Szyszko
authors.forename: Natasza
authors.initials: N
authors.lastname: Sprutta
authors.forename: Paulina
authors.initials: P
authors.lastname: Chwalisz
authors.forename: Marcin
authors.initials: M
authors.lastname: Stępień
authors.forename: Lechosław
authors.initials: L
authors.lastname: Latos-Grażyński
keywords: NMR spectroscopy; aromaticity; conjugation; density functional calculations; porphyrinoids