Title: Ring currents in the porphyrins: pi shielding, delocalisation pathways and the central cation
Authors: Steiner, E ×
Soncini, Alessandro
Fowler, PW #
Issue Date: Jan-2005
Publisher: Royal soc chemistry
Series Title: Organic & biomolecular chemistry vol:3 issue:22 pages:4053-4059
Abstract: It is shown that the ipsocentric orbital-based model explains how the charge of the central cation drives the delocalisation pathway in metalloporphyrins. A positive charge +Ze at the centre of the porphin ring gives rise to a two-way radial transfer of charge within the it structure of the porphin macrocycle. This manifests itself in a change of pathway of the global pi current, as Z increases from Z = 0, from an inner- through a bifurcated- to an outer-pathway. Changes of pathway can be interpreted in terms of a specific pi shielding effect whereby electrons in high-lying pi orbitals are screened from the central charge by the electrons in lower-lying orbitals of the same symmetry. These changes in pi structure are essentially independent of accompanying changes in the a structure.
ISSN: 1477-0520
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
× corresponding author
# (joint) last author

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