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.

中文翻译：

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二苯基苯并[k]荧蒽的阳极偶联：利用循环伏安法和电化学发光的机理和动力学研究。

在铂电极上氧化后，（7,12-二苯基）苯并[k]荧蒽（1）进行分子间脱氢偶联形成双-4,4'-（7,12-二苯基）苯并[k]荧蒽（2） 。该产物的进一步氧化导致分子内偶联反应缓慢得多，从而产生二苯并{[f，f']-4,4'，7,7'-四苯基}二茚基[1,2,3-cd：1'，2 '，3'-lm] per（3）。2可以通过1的本体电解以及4-溴-7,12-二苯基苯并[k]荧蒽（4）与镍催化剂的化学偶联来合成。化合物1-3能够进行电化学发光（ECL），并且已检测到它们的偶联反应，并使用此技术进行跟踪。已对1的循环伏安图进行了数字模拟，以提供有关初始分子间氧化偶联反应的机理和动力学见解。证据支持EC（2）（）EE机制，其中自由基1的耦合是限速步骤。通过将实验数据拟合至理论工作曲线，已确定二聚过程的二阶速率常数k = 7500 M（-）（1）s（-）（1）。