Liquid-phase ESR, ENDOR, and TRIPLE resonance of porphycene anion radicals

• Published in: Journal of the American Chemical Society Vol. 112; no. 18; pp. 6463 - 6471
• Main Authors: Schluepmann, Jenny, Huber, Martina, Toporowicz, Moshe, Plato, Martin, Koecher, Matthias, Vogel, Emanuel, Levanon, Haim, Moebius, Klaus
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01.08.1990
• Subjects: 140505 - Solar Energy Conversion- Photochemical, Photobiological, & Thermochemical Conversion- (1980-); 400201 - Chemical & Physicochemical Properties; ANIONS; AQUEOUS SOLUTIONS; Atomic and molecular physics; AZOLES; CALCULATION METHODS; CARBOXYLIC ACIDS; CHARGED PARTICLES; COUPLING CONSTANTS; DISPERSIONS; ELECTRON SPIN RESONANCE; Exact sciences and technology; HETEROCYCLIC ACIDS; HETEROCYCLIC COMPOUNDS; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; IONS; ISOMERS; MAGNETIC RESONANCE; MIXTURES; MOLECULAR ORBITAL METHOD; Molecular properties and interactions with photons; Multiple resonances (including double and higher-order resonance processes, such as double nuclear magnetic resonance, electron double resonance and microwave optical double resonance); ORGANIC ACIDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; Physics; PORPHYRINS; PYRROLES; RESONANCE; SOLAR ENERGY; SOLUTIONS; STRUCTURAL CHEMICAL ANALYSIS; Liquid state; Hyperfine coupling constant; Nitrogen heterocycle; G factor; Theoretical study; Spin density; Experimental study; Macrocycle; Organic free radical; SCF MO method; EPR spectrum; ENDOR spectrum; Organic compounds; Conformation
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja00174a002

Porphycenes are novel structural isomers of porphyrins. The radical anions of several porphycenes were studied by ESR, ENDOR, and TRIPLE resonance in liquid solution yielding the isotropic hyperfine coupling constants including signs. For the unsubstituted free-base porphycene, the 2,7,12,17-tetra-n-propylporphycene, and the 9,10,19,20-tetra-n-propylporphycene, the experimental findings are compared with results of all-valence-electrons self-consistent field molecular orbital calculations (RHF-INDO/SP).