title: Metalated Hexaphyrins: From Understanding to Rational Design.
abstract: The heretofore unpredictable behavior of [26] and [28]hexaphyrins upon metalation has been elucidated through quantum chemical calculations. It is demonstrated that the molecular topology of Group 10 and Group 11 metal complexes of hexaphyrins depends on sensitive interplay between the intrinsic ligand strain and the metal-ligand interaction strength. As such, the aromaticity of the ligand and effective charge of the metal are revealed as key factors determining the binding mode and the preference for Möbius or Hückel structures. These findings offer a new perspective to rationalize experimental observations for metalated hexaphyrins. More importantly, the proposed guidelines could be useful for designing novel complexes of hexaphyrins, such as a hitherto unknown Möbius [26]hexaphyrin complex.
authors.affiliation: Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050 Brussels (Belgium). malonsog@vub.ac.be.
authors.forename: Mercedes
authors.initials: M
authors.lastname: Alonso
authors.affiliation: Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050 Brussels (Belgium).
authors.forename: Balazs
authors.initials: B
authors.lastname: Pinter
authors.affiliation: Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050 Brussels (Belgium).
authors.forename: Paul
authors.initials: P
authors.lastname: Geerlings
authors.affiliation: Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050 Brussels (Belgium).
authors.forename: Frank
authors.initials: F
authors.lastname: De Proft
keywords: aromaticity; chemical topology; conformation analysis; metalation; porphyrinoids