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Metalated Hexaphyrins: From Understanding to Rational Design
Author(s) -
Alonso Mercedes,
Pinter Balazs,
Geerlings Paul,
De Proft Frank
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201502894
Subject(s) - metalation , ligand (biochemistry) , metal , computational chemistry , chemistry , rational design , group (periodic table) , topology (electrical circuits) , stereochemistry , chemical physics , materials science , nanotechnology , mathematics , organic chemistry , receptor , biochemistry , combinatorics
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.