Naphthalenyl, Anthracenyl, Tetracenyl, and Pentacenyl Radicals and Their Anions

• DOI: 10.1021/jp030494x
• Publication Date: 2003-08-07T13:11:55Z
• Authors: Brian N. Papas; Suyun Wang; Nathan J. DeYonker; Henry L. Woodcock; Henry F. Schaefer
• Keywords: Tetracene

Electronic structure theory has been applied to the naphthalene-, anthracene-, tetracene-, and pentacene-based radicals their anions. Five different density functional methods were used predict adiabatic electron affinities for these radicals. A consistent trend was found, suggesting that affinity at a site of hydrogen removal is primarily dependent upon steric effects polycyclic aromatic hydrocarbons. The results 1-naphthalenyl 2-naphthalenyl compared experiment, it found B3LYP appears be most reliable this type system. For larger systems predicted specific are 1.51 eV (1-anthracenyl), 1.46 (2-anthracenyl), 1.68 (9-anthracenyl); 1.61 (1-tetracenyl), 1.56 (2-tetracenyl), 1.82 (12-tetracenyl); 1.93 (14-pentacenyl), 2.01 (13-pentacenyl), (1-pentacenyl), 1.63 (2-pentacenyl). These 0.5−1.5 higher than those analogous closed-shell singlet hydrocarbons (PAHs); i.e., EA(anthracene) = 0.53 eV. global minimum each radical does not have same removed as anion. With in mind, (or preferred site) AEAs 1.37 (naphthalenyl), 1.64 (anthracenyl), 1.81 (tetracenyl), 1.97 (pentacenyl).