Investigation of excited state electron-transfer reactions. A search for other associative processes

Abstract

Abstract The present investigations were carried out to reveal the nature of the photoinduced electron-transfer (ET) process within the electron donors 1,2,3,4-tetrahydroquinoline (THQ) and 1-methyl-1,2,3,4-tetrahydroquinoline (THMe), and widely used acceptor tetracyanoquinodimethane (TCNQ) in the highly polar solvent acetonitrile (ACN) at 300 K. Observations of considerable overlapping between the emission spectrum of the donor molecules studied in the present investigation and the electronic absorption spectrum of the acceptor TCNQ, coupled to a high negative value of Δ G [the energy gap between the locally excited (LE) and radical ion pair (RIP) states] when one of the chromophores is excited, indicate the possibility of concurrent occurrence of the two processes, e.g. energy and electron transfer. Surprisingly even when the donor chromophore is photoexcited, no spectral manifestation of energy transfer was observed, though both steady state and time resolved (in the time domain of nanosecond order) spectroscopic measurements strongly suggest the occurrence of a highly exothermic ET reaction within the present donor—acceptor systems. Furthermore such ET reactions have been suggested to occur between donor and acceptor separated by a large distance ( ∼ 7 A), and quenching of fluorescence emission of donor molecules is caused primarily due to outer sphere ET reactions with the acceptor. Measured electron transfer rates ( k ET ) were found to be of much lower value ( ∼ 10 7 s −1 ). It is demonstrated that loose structure of the transient geminate ion pair complex is formed due to the encounter between excited acceptor (or donor) and unexcited donor (or acceptor), and due to this structural property, a stable anionic species (TCNQ − ion) is produced due to the rapid dissociation (probably in the picosecond time domain) of this excited complex. It is hinted that synthesis of biochromophoric systems in which the present donor and acceptor chromophore would be linked by a polymethylene type (σ-type) spacer might be useful in building good photoconducting materials.