Article

Electron transfer at the single-molecule level in a triphenylamine-perylene imide molecule.

Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, 3001 Heverlee, Belgium.
ChemPhysChem (Impact Factor: 3.35). 06/2005; 6(5):942-8. DOI:10.1002/cphc.200400567
Source: PubMed

ABSTRACT Photoinduced electron transfer (ET) processes in a donor-acceptor system based on triphenylamine and perylene imide have been studied at the single-molecule (SM) and ensemble levels. The system exists as two isomers, one of which undergoes forward and reverse ET in toluene with decay constants of 3.0 and 2.2x10(9) s(-1), respectively, resulting in the dual emission of quenched and delayed fluorescence while the other isomer remains ET-inactive. The fluorescence of both isomers is heavily quenched in the more polar solvent, diethyl ether, by ET. A broad range of ET dynamics is seen at the SM level in polystryene with the two isomers nonresolvable indicating that the local nanoenvironment of the SMs varies considerably throughout the polymer matrix. Both the electronic coupling and the driving force for ET are shown to influence the ET dynamics. Many fluorescence trajectories of SMs show long periods (tens of milliseconds to seconds) where the count rate is attenuated either partly (a "dim" state) or to the background level (an "off-time"). During these periods, the reduction or interruption of emission is attributed to cycles of rapid charge separation followed by charge recombination to the ground state reducing the fluorescence quantum yield of the SM.

0 0
 · 
0 Bookmarks
 · 
83 Views
  • [show abstract] [hide abstract]
    ABSTRACT: Nanostructured metal oxide semiconductors, such as TiO(2) and ZnO, have attracted great attention as the promising material for photovoltaic devices, photocatalysts for water splitting and environmental purification, sensors, batteries, etc. In this critical review, we have focused on the on-site observation of interfacial chemical reactions involving charge carriers and reactive oxygen species (ROS), such as singlet oxygen and the hydroxyl radical, generated by the photoexcitation of TiO(2) nanoparticles using single-molecule, single-particle fluorescence spectroscopy. Advanced fluorescence imaging techniques enable us to determine the location of the photocatalytically active sites that are closely related to the defects heterogeneously distributed on the surface. Consequently, this review provides a great opportunity to understand the temporal and spatial heterogeneities within an individual catalyst particle, allowing for the potential use of single-molecule, single-particle approaches in the analysis of photocatalytic reactions (189 references).
    Chemical Society Reviews 12/2010; 39(12):4802-19. · 24.89 Impact Factor
  • [show abstract] [hide abstract]
    ABSTRACT: A new core-substituted naphthalene diimide (cNDI) compound that is sensitive to both H(+) and solvent polarity has been synthesised and characterised. Optical absorption and emission change upon protonation while emission quantum yield and decay kinetics of the unprotonated form vary significantly with solvent polarity due to delayed fluorescence.
    Chemical Communications 04/2013; · 6.38 Impact Factor
  • [show abstract] [hide abstract]
    ABSTRACT: We recorded fluorescence time traces, and simultaneously either the fluorescence lifetime or the emission spectra from single perylene bisimide (PBI) dimers embedded in a polystyrene matrix. In these traces three distinct intensity levels can be distinguished, which reflect the photo-induced radicalisation of one of the perylene subunits. Differences in the energy transfer rate between the neutral PBI and the reversibly formed radical anion give rise to variations in the chronological order of the appearance of the intensity levels, which allowed us to categorise the time traces into three distinct groups: Type 1 blinking corresponds to a high energy transfer rate, type 2 blinking to fluctuations between large and small transfer rates (dynamic quenching), and type 3 blinking results from small energy transfer rates together with Coulomb blockade. The information that we obtain from the distributions of the fluorescence lifetimes at the various signal levels allows us to relate these differences to properties of the local polymer environment of the dimers.
    Physical Chemistry Chemical Physics 07/2012; 14(30):10789-98. · 3.83 Impact Factor

Full-text (2 Sources)

View
45 Downloads
Available from
Dec 22, 2012