Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 7, Pages 2936-2947Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201404230
Keywords
cyclic voltammetry; dendrimers; electrochemiluminescence; electron transfer; quantum chemical calculations
Categories
Ask authors/readers for more resources
The electrochemistry, photophysics, and electrochemically generated chemiluminescence (ECL) of a family of polysulfurated dendrimers with a pyrene core have been thoroughly investigated and complemented by theoretical calculations. The redox and luminescence properties of dendrimers are dependent on the generation number. From low to higher generation it is both easier to reduce and oxidize them and the emission efficiency increases along the family, with respect to the polysulfurated pyrene core. The analysis of such data evidences that the formation of the singlet excited state by cation-anion annihilation is an energy-deficient process and, thus, the ECL has been justified through the triplet-triplet annihilation pathway. The study of the dynamics of the ECL emission was achieved both experimen-tally and theoretically by molecular mechanics and quantum chemical calculations. It has allowed rationalization of a possible mechanism and the experimental dependence of the transient ECL on the dendrimer generation. The theoretically calculated Marcus electron-transfer rate constant compares very well with that obtained by the finite element simulation of the whole ECL mechanism. This highlights the role played by the thioether dendrons in modulating the redox and photophysical properties, responsible for the occurrence and dynamics of the electron transfer involved in the ECL. Thus, the combination of experimental and computational results allows understanding of the dendrimer size dependence of the ECL transient signal as a result of factors affecting the annihilation electron transfer.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available