title: Efficient emission from charge recombination during the pulse radiolysis of electrochemical luminescent donor-acceptor molecules with an ethynyl linkage.
abstract: Efficient monomer and excimer emission from various donor-acceptor substituted phenylethynes (PE), 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 PE in the singlet excited state (1PE*) and the excimer (1PE2*) can be interpreted by the charge recombination between the PE radical cation (PE.+) and the PE radical anion (PE.-) which are generated initially from the radiolytic reaction 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 (-DeltaH' degrees ) and singlet excitation energies of donor-substituted phenyl(9-acridinyl)ethynes (1(a-e)). In addition to the monomer emission, the compounds bearing weak donors (1(a-d)) show the excimer emission due to a very small twist angle between the donor and acceptor moieties. For the phenyl(9-cyano-10-anthracenyl)ethynes (2(c) and 2(f)), although they also show the monomer and excimer emissions, it cannot be explained by the relationship between -DeltaH' degrees values and their singlet excitation energies, suggesting the formation of the ICT state and H-type excimer in which two 9-cyano-10-anthracenyl moieties are stacked face-to-face with donor bearing a benzene ring projecting perpendicularly away from each other through the charge recombination between 2.+) and 2.-) and/or triplet-triplet annihilation.
authors.affiliation: Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
authors.forename: Shingo
authors.initials: S
authors.lastname: Samori
authors.forename: Sachiko
authors.initials: S
authors.lastname: Tojo
authors.forename: Mamoru
authors.initials: M
authors.lastname: Fujitsuka
authors.forename: Shu-Wen
authors.initials: SW
authors.lastname: Yang
authors.forename: Arumugasamy
authors.initials: A
authors.lastname: Elangovan
authors.forename: Tong-Ing
authors.initials: TI
authors.lastname: Ho
authors.forename: Tetsuro
authors.initials: T
authors.lastname: Majima