Magneto-structural relationships for radical cation and neutral pyridinophane structures with intrabridgehead nitrogen atoms. An integrated experimental and quantum mechanical study.
An integrated experimental and computational approach was used to compare the properties of representative molecules containing intrabridgehead nitrogen atoms with those of the corresponding radical cations issuing from one-electron oxidation with the aim of unraveling the characteristics of the three-electron sigma-bonds formed in the open-shell species. From a quantitative point of view, last-generation density functional methods coupled with proper basis sets and, when needed, continuum models for describing bulk solvent effects confirm their reliability for the computation of structures and magnetic properties of organic free radicals. From an interpretative point of view, different hybridizations of nitrogen atoms tuned by their chemical environment lead to markedly different magnetic properties that represent reliable and sensitive probes of structural and electronic characteristics.
Williams
Ffrancon
F
Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996-1600, USA. williams@ion.chem.utk.edu
Chen
Guo-Fei
GF
Mattar
Saba M
SM
Scudder
Paul H
PH
Trieber
Dwight A
DA
Saven
Jeffery G
JG
Whritenour
David C
DC
Cimino
Paola
P
Barone
Vincenzo
V
D019281:Dimerization; D004563:Electrochemistry; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000737:chemistry; D008280:Magnetics; D009584:Nitrogen / Q000737:chemistry*; D010084:Oxidation-Reduction; D011725:Pyridines / Q000737:chemistry*; D011789:Quantum Theory
D005609:Free Radicals; D011725:Pyridines; D009584:Nitrogen; C023666:pyridine