Magneto-Structural Relationships for Radical Cation and Neutral Pyridinophane Structures with Intrabridgehead Nitrogen Atoms. An Integrated Experimental and Quantum Mechanical Study
| Autor: | Dwight A Trieber, Jeffery G Saven, Ffrancon Williams, David C Whritenour, Paola Cimino, Saba M Mattar, Vincenzo Barone, Guo-Fei Chen, Paul H. Scudder |
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| Rok vydání: | 2009 |
| Předmět: |
Free Radicals
Nitrogen Pyridines Chemistry Radical Electron Spin Resonance Spectroscopy Nanoparticle Electrochemistry Surfaces Coatings and Films Magnetics Radical ion Chemical physics Materials Chemistry Quantum Theory Molecule Physical chemistry Self-assembly Soft matter Physics::Chemical Physics Physical and Theoretical Chemistry Solvent effects Dimerization Oxidation-Reduction |
| Zdroj: | The Journal of Physical Chemistry B. 113:9026-9034 |
| ISSN: | 1520-5207 1520-6106 |
| DOI: | 10.1021/jp902493e |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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