Anodic Coupling of Diphenylbenzo[k]fluoranthene:  Mechanistic and Kinetic Studies Utilizing Cyclic Voltammetry and Electrogenerated Chemiluminescence

Abstract

Upon oxidation at a platinum electrode, (7,12-diphenyl)benzo[k]fluoranthene (1) undergoes intermolecular dehydrogenative coupling to form bis-4,4'-(7,12-diphenyl)benzo[k]fluoranthene (2). Further oxidation of this product results in a much slower intramolecular coupling reaction that yields dibenzo{[f,f']-4,4',7,7'-tetraphenyl}diindeno[1,2,3-cd:1',2',3'-lm]perylene (3). 2 can be synthesized via bulk electrolysis of 1 and also by the chemical coupling of 4-bromo-7,12-diphenylbenzo[k]fluoranthene (4) with a nickel catalyst. Compounds 1-3 are capable of electrogenerated chemiluminescence (ECL), and their coupling reactions have been detected and followed using this technique. Cyclic voltammograms of 1 have been digitally simulated to provide mechanistic and kinetic insight into the initial intermolecular oxidative coupling reaction. Evidence supports an EC(2)()EE mechanism, in which the coupling of radical cations of 1 is the rate-limiting step. A second-order rate constant of k = 7500 M(-)(1) s(-)(1) has been determined for the dimerization process by fitting experimental data to theoretical working curves.

Electrogenerated chemiluminescence 73: acid–base properties, electrochemistry, and electrogenerated chemiluminescence of neutral red in acetonitrile

“…A Pt wire and a silver (Ag) wire were employed as the auxiliary electrode and the quasi-reference electrode (QRE), respectively. All electrode potentials were calibrated by using the ferrocene (Fc)/ferrocenium (Fc + ) redox couple and converted to V vs SCE by taking E (Fc/Fc + ) = 0.424 V vs SCE [18]. All electrodes were polished with 0.05 lm alumina suspension (Buehler, Lake Bluff, IL), and sonicated in deionized water and ethanol.…”

Aryl-diamide bridged binuclear ruthenium (II) tris(bipyridine) complexes: Synthesis, photophysical, electrochemical and electrochemiluminescence properties

“…Typically, aromatic hydrocarbons [2] and their derivatives [3] are used either by themselves or by the incorporation to a metal complex [4] as an ECL candidate. One of the most widely used metal complexes is the ruthenium tris(bipyridine) [Ru(bpy) 3 ] 2+ [5].…”

Multifunctional Diarylamine-Substituted Benzo[k]fluoranthene Derivatives as Green Electroluminescent Emitters and Nonlinear Optical Materials

“…The precursor 3-bromo-7,12-diphenylbenzo[k]fluoranthene and 3-bromo-7,12-di(1-naphthyl)benzo[k]fluoranthene were synthesized according to the literature procedures. 15 The solvents in the reactions were dried by using routine procedures. All other reagents in the scheme were used as received from commercial sources.…”