Single-molecule spectroscopy of molecular aggregates at low temperature

We have conducted single-molecule spectroscopy of a fluorescent polyphenylene dendrimer consisting of four peripheral perylenemonoimides which serve as energy donors and a central terrylenediimide which is the energy acceptor. After selective excitation of the donors the low-temperature emission spectra of single dendrimers show the purely electronic zero-phonon line as the most prominent feature of the acceptor. These sharp emission lines are subjected to appreciable spectral shifts. Fluorescence excitation spectroscopy of individual dendrimers in the spectral region of the donor absorption allows to extract energy transfer rates for single donors within the dendrimer. Although the energy …

Single molecule spectroscopy of multichromophoric assemblies

We have investigated multichromophoric assemblies composed of a variable number of chromophores by single molecule spectroscopy. Specific spectral signatures have allowed to distinguish at the single molecule level between molecular dimers representing strong and weak electronic dipole-dipole coupling. By using fluorescence excitation spectroscopy at low temperature, the sharp purely electronic zero-phonon lines of single chromophores within a single dendrimer containing four chromophores could be isolated in the frequency domain.

Chapter 2 Single molecule spectroscopy of multichromophoric dendrimers at room and liquid helium temperatures

Publisher Summary This chapter discusses the single molecule spectroscopy of multichromophoric dendrimers at room and liquid helium temperatures. Single molecule spectroscopy has become an important tool for the optical study of the electronic interactions of proximate chromophores as the electronic interactions can be studied without averaging over the properties of an intrinsically heterogeneous ensemble. Single perylenemonoimide (PMI) chromophores are selectively addressed in the frequency domain within spatially isolated multichromophoric dendrimers, which are dispersed in a polymer film. Although the chromophores are interacting, they still can be addressed separately. This feature in …

Energy transfer rates and pathways of single donor chromophores in a multichromophoric dendrimer built around a central acceptor core.

An artificial light-harvesting dendrimer showing highly efficient electronic excitation energy transfer from four peripheral donors to one central acceptor has been investigated by single-molecule spectroscopy at low temperatures. Confocal imaging in combination with frequency selective excitation spectroscopy gives direct access to energy transfer rates of individual donors and allows the determination of energy transfer pathways within a single multichromophoric aggregate.

Watching the photo-oxidation of a single aromatic hydrocarbon molecule

International audience; The photooxidation of single dye molecules (see scheme) can be followed by confocal fluorescence microscopy. The self-sensitized reaction with singlet oxygen leads to a suite of products, which may be differentiated spectrally. Tentative structures for certain photoproducts have been obtained from quantum-chemical calculations.

Single-Molecule Optical Switching: A Mechanistic Study of Nonphotochemical Hole-Burning

Persistent spectral hole-burning of dopant chromophores embedded in solid matrices has proven to be a sensitive high-resolution spectroscopic tool to investigate structural and dynamic properties of amorphous and crystalline hosts at low temperature [1]. A commonly encountered mechanism of holeformation is the nonphotochemical process, for which it is assumed that the frequency selective laser excitation and the subsequent relaxation of guest and host eventually leads to a change of configurational degrees of freedom in the nearby environment of the photo-excited centers or in the impurities themselves (or both) [2]. However, detailed knowledge about the microscopic mechanism of the nonphot…

Frequency selective excitation of single chromophores within shape-persistent multichromophoric dendrimers

Isolated multichromophoric dendrimers containing four perylenemonoimide chromophores were investigated in a confocal microscope which allowed imaging of the same set of dendrimers over a wide temperature range. Emission spectra at low temperature (2 K) reveal narrow zero-phonon lines although the electron-phonon coupling is not negligible. By using fluorescence excitation spectroscopy, the sharp purely electronic zero-phonon lines of single chromophores within a single multichromophoric unit could be isolated in the frequency domain. Selective excitation into a higher energy chromophoric site is followed by rapid directional energy transfer into the lowest energy site from which emission th…

Fluoreszenzmikroskopische Verfolgung des photooxidativen Abbaus eines einzelnen aromatischen Kohlenwasserstoffmoleküls