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Electron transfer (ET) in the extended 1, 1 ' -bipyridinium has been investigated by UV Nis/NIR and EPR in-situ spectroelectrochemical techniques. During the in-situ cyclic voltammetric scan no EPR signal was observed at the potential corresponding to the first electron transfer at room temperature, whereas the EPR signal for the subsequent ET steadily increased and was observed even at the potentials corresponding to the fourth electron transfer. The EPR signal was detected for the first electron transfer step only at elevated temperature. The evidence for the presence of comproportionation processes and for the formation of n-dimer is discussed
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