TY  - JOUR
A1  - Titov, Evgenii
A1  - Lysyakova, Liudmila
A1  - Lomadze, Nino
A1  - Kabashin, Andrei V.
A1  - Saalfrank, Peter
A1  - Santer, Svetlana
T1  - Thermal Cis-to-Trans Isomerization of Azobenzene-Containing Molecules Enhanced by Gold Nanoparticles: An Experimental and Theoretical Study
T2  - The journal of physical chemistry : C, Nanomaterials and interfaces
N2  - We report on the experimental and theoretical investigation of a considerable increase in the rate for thermal cis -> trans isomerization of azobenzene-containing molecules in the presence of gold nanopartides. Experimentally, by means of UV vis spectroscopy, we studied a series of azobenzene-containing surfactants and 4-nitroazobenzene. We found that in the presence of gold,nanoparticles the thermal lifetime of the cis isomer of the azobenzenecontaining molecules was decreased by up to 3 orders of magnitude in comparison to the lifetime in solution without nanoparticles. The electron transfer between azobenzene-containing molecules and a surface of gold nanopartides is a possible reason to promote the thermal cis trans switching. To investigate the effect of electron attachment to, and withdrawal from, the azobenzene-containing molecules on the isomerization rate, we performed density functional theory calculations of activation energy barriers of the reaction together with Eyring's transition state theory calculations of the rates for azobenzene derivatives with donor and acceptor groups in para position of one of the phenyl rings, as well as for one of the azobenzene-containing surfactants. We found that activation barriers are greatly lowered for azobenzene-containing molecules, both upon electron attachment and withdrawal, which leads, in turn, to a dramatic increase in the thermal isomerization rate.
Y1  - 2015
UR  - https://publishup.uni-potsdam.de/frontdoor/index/index/docId/38740
SN  - 1932-7447
VL  - 119
IS  - 30
SP  - 17369
EP  - 17377
PB  - American Chemical Society
CY  - Washington
ER  -