Efficient Emission from Charge Recombination during the Pulse Radiolysis of Electrochemical Luminescent Substituted Quinolines with Donor-Acceptor Character

摘要

Efficient emission from various donor-acceptor quinolines with an ethynyl linkage(PnQ),which are known as efficient electrogenerated chemiluminescent molecules,was observed with time-resolved fluorescence measurement during the pulse radiolysis in benzene.On the basis of the transient absorption and emission measurements,and steady-state measurements,the formation of PnQ in the singlet excited state can be interpreted by charge recombination between the PnQ radical cation and the PnQ radical anion which are generated initially from the radiolytic reaction in benzene.The strong electronic coupling between the donor and acceptor through conjugation is responsible for the efficient emission during the pulse radiolysis of PnQ in benzene.It is suggested that the positive and negative charges are localized on the donor and acceptor moieties in the radical cation and anion,respectively.This mechanism is reasonably explained by the relationship between the annihilation enthalpy changes and singlet excitation energies of PnQ.The formation of the intramolecular charge transfer state is assumed for PnQ in the singlet excited state with a strong electron donating substituent.The emission from PnQ is suggested to originate from PnQ in the singlet excited state formed from the charge recombination between the PnQ radical cation and the PnQ radical anion during the pulse radiolysis.This is strong evidence for the efficient electrogenerated chemiluminescence of PnQ.