title: Primary electron-transfer dynamics in 2-phenylindole-9-cyanoanthracene system. A comparative study with 2-methylindole.
abstract: Electrochemical measurements by cyclic voltammetry predict the possibility of occurrence of photoinduced electron-transfer (PET) reactions between the ground state of 2-phenylindole (2PI) (electron donor) and the excited singlet of 9-cyanoanthracene (9CNA) molecule acting as an electron acceptor. However, 2PI should be expected to behave as a relatively weaker electron donating agent than the structurally related donor 2-methylindole (2MI) as it possesses higher oxidation potential value. Both steady-state and time-resolved spectroscopic measurements in the polar acetonitrile (ACN) and ethanol (EtOH) solvents show that the fluorescence quenching phenomenon of 9CNA in presence of 2PI is primarily due to the involvement of dynamic process which in high probability should be PET. Nevertheless, in less polar tetrahydrofuran (THF) medium, the quenching of 9CNA results from the combined effect of dynamic and static modes. The transient absorption spectra, measured by using nanosecond laser flash photolysis, of 9CNA in presence of 2PI exhibit the signature of the bands of the anionic species of 9CNA, cation of the donor 2PI and the contact neutral radical. Observations of the transient absorption at the different delays infer that ion-recombination mechanism is responsible for production of the monomeric triplets of both 9CNA and 2PI. From the transient absorption decays in ACN medium, it has been demonstrated that the diffusional separation of ions from geminate ion-pair is facilitated in the case of 2MI-9CNA pair whereas for 2PI-9CNA system the energy wasting charge recombination dominates over the process of charge dissociation. From the above observations, the possibility of developing much potential photosynthetic model compounds with the donor 2MI, rather than with the other donor 2PI molecule has been hinted.
authors.affiliation: Department of Spectroscopy, Indian Association for the Cultivation of Science, 2A B. Raja S.C. Mullick Road, Jadavpur, Kolkata 700032, India.
authors.forename: T
authors.initials: T
authors.lastname: Bhattacharya
authors.forename: S K
authors.initials: SK
authors.lastname: Pal
authors.forename: T
authors.initials: T
authors.lastname: Misra
authors.forename: R D
authors.initials: RD
authors.lastname: Saini
authors.forename: T
authors.initials: T
authors.lastname: Ganguly
mesh_terms: D000873:Anthracenes / Q000737:chemistry*; D004563:Electrochemistry; D004579:Electron Transport; D007211:Indoles / Q000737:chemistry*; D007834:Lasers; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010777:Photochemistry; D010782:Photolysis; D013050:Spectrometry, Fluorescence; D013053:Spectrophotometry; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000873:Anthracenes; D007211:Indoles; C022958:2-methylindole