Investigations on nonradiative transitions in different environments using excited (or ground state) 1,2,3,4-tetrahydroquinoline (THQ) as donor and ground state (or excited) 9-fluorenone (9FL) or 2-nitro-9-fluorenone (2N9FL) as acceptors

Abstract

By using steady state and time resolved spectroscopic techniques, investigations were made on the nature and mechanisms of different nonradiative processes involved within the excited donor (or acceptor) and ground state acceptor (or donor) in nonpolar n-heptane (NH), polar protic ethanol (EtOH), and polar aprotic acetonitrile (ACN) solvents at the ambient temperature as well as in EtOH rigid glassy matrix at 77 K. The bicyclic molecule 1,2,3,4-tetrahydroquinoline (THQ) was used as a donor (D) in the present investigation whereas 9-fluorenone (9FL) and 2-nitro-9-fluorenone (2N9FL) were chosen as electron acceptors (A). When the donor chromophore was excited in presence of an acceptor, highly exothermic electron transfer (ET) reactions seemed to occur from observed large negative driving energy (deltaG0) values, measured by electrochemical techniques, Förster's type energy transfer, static quenching, etc. An attempt was made to estimate separately the contributions of static and dynamic quenching modes in the overall quenching mechanism of donor fluorescence by using a model of modified Stern-Volmer (SV) relation. From this relation it seemingly indicated that the major contribution in quenching originated from the static mode. When excited acceptors react with the ground state donor THQ it is primarily ET reactions that seem to occur. Observations of the transient absorption spectra, by laser flash photolysis techniques, of contact ion-pairs of the present D-A systems along with the triplet absorption spectra of the monomeric acceptor (9FL and 2N9Fl) corroborate our views regarding the occurrence of photoinduced ET reactions within the present reacting systems. At 77 K the combined effect of Förster type energy transfer and static quenching seems to be responsible for observed lowering of donor fluorescence emission intensity in presence of acceptors (9FL or 2N9FL). However, the phosphorescence lifetime measurements reveal that the triplet donor might be involved in photoinduced ET reaction with the unexcited acceptor in rigid glassy matrix at 77 K and this possibly causes the reduction in the phosphorescence band intensity of the donor THQ in presence of the latter one. Key words: electron transfer, static quenching, fluorescence quenching, phosphorescence, energy transfer.