title: Three-dimensional energy transport in highly luminescent host-guest crystals: a quantitative experimental and theoretical study.
abstract: We present a combined experimental and theoretical study on energy transfer processes in a well-defined three-dimensional host-guest system, which allows for high chromophore concentrations while maintaining the highly luminescent properties of the molecules in solution. The self-assembled, nanostructured system with a defined ratio of included donor and acceptor molecules is amenable to quantitative comparison between experiment and theory. Experimentally, energy migration is monitored by steady-state and time-resolved fluorescence spectroscopy. From the theoretical side, the energy transfer process is modeled by a Monte Carlo approach including homo and hetero transfer steps with multi-acceptor distribution. In this dense system, the classical Förster point-dipole approach for energy transfer breaks down, and the hopping rates are therefore calculated on the basis of a quantum-chemical description of the donor and acceptor excited states. Thereby, the true directionality of the excitation diffusion is revealed. Excellent agreement with experimental donor and acceptor decays and overall transfer efficiencies is found. Even at low acceptor concentrations (down to 0.1%), efficient energy transfer over distances as large as 25 nm was observed due to rapid energy migration through a series of homo-transfer steps with preference along one direction of the structure.
authors.affiliation: Institute of Physical and Theoretical Chemistry, University of Tübingen, Auf der Morgenstelle 8, D-72076 Tübingen, Germany.
authors.forename: Lars
authors.initials: L
authors.lastname: Poulsen
authors.forename: Mikael
authors.initials: M
authors.lastname: Jazdzyk
authors.forename: Jean-Edouard
authors.initials: JE
authors.lastname: Communal
authors.forename: Juan Carlos
authors.initials: JC
authors.lastname: Sancho-García
authors.forename: Andrea
authors.initials: A
authors.lastname: Mura
authors.forename: Giovanni
authors.initials: G
authors.lastname: Bongiovanni
authors.forename: David
authors.initials: D
authors.lastname: Beljonne
authors.forename: Jérôme
authors.initials: J
authors.lastname: Cornil
authors.forename: Michael
authors.initials: M
authors.lastname: Hanack
authors.forename: Hans-Joachim
authors.initials: HJ
authors.lastname: Egelhaaf
authors.forename: Johannes
authors.initials: J
authors.lastname: Gierschner