Förster Resonant Energy Transfer in Orthogonally Arranged Chromophores

Langhals, Heinz; Esterbauer, Andreas J.; Walter, A.; Riedle, Eberhard; Pugliesi, Igor

doi:10.1021/ja101544x

Cited by 107 publications

(156 citation statements)

References 31 publications

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“…Molecular addressing in the visible region (about 0.6 PHz) with operating chromophores with dimension of about 1 nm can be basically performed by means of electric dipole-dipole interactions where a theoretical concept was developed by Perrin [8] and further extended by Förster [9][10][11][12] (Förster resonance energy transfer, FRET) having established equation (1) for the quantitative description of the distance function R. For more recent discussion see [13]. …”

Section: Resultsmentioning

confidence: 99%

A Concept for Molecular Addressing by Means of Far-reaching Electromagnetic Interactions in the Visible

Langhals¹

2017

J Electr Electron Syst

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Section: Resultsmentioning

confidence: 99%

A Concept for Molecular Addressing by Means of Far-reaching Electromagnetic Interactions in the Visible

Langhals¹

2017

J Electr Electron Syst

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“…Our results show EET can be much faster than previous studies have observed on different perpendicularly held molecular dyads. 8,10 Other intriguing observations relate to the non-equilibrium geometry of the donor and the lack of correlation between rate of EET and degree of spectral overlap. It has been reported, 37 however, that the strict requirement of spectral overlap between the donor emission spectrum and the acceptor absorption spectrum is relaxed if modes couple simultaneously to the donor and acceptor electronic excitations with opposite sign displacements.…”

Section: Discussionmentioning

confidence: 99%

Ultrafast Electronic Energy Transfer Beyond the Weak Coupling Limit in a Proximal but Orthogonal Molecular Dyad

et al. 2015

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Electronic energy transfer (EET) from a donor to an acceptor is an important mechanism that controls the light harvesting efficiency in a wide variety of systems, including artificial and natural photosynthesis and contemporary photovoltaic technologies. The detailed mechanism of EET at short distances or large angles between the donor and acceptor is poorly understood. Here the influence of the orientation between the donor and acceptor on EET is explored using a molecule with two nearly perpendicular chromophores. Very fast EET with a time constant of 120 fs is observed, which is at least forty times faster than the time predicted by Coulombic coupling calculations. Depolarization of the emission signal indicates that the transition dipole rotates through ca. 64 0 , indicating the near orthogonal nature of the EET event. The rate of EET is found to be similar to structural relaxation rates in the photo-excited oligothiophene donor alone, which suggests that this initial relaxation brings the dyad to a conical intersection where the excitation jumps to the acceptor.

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“…In further pump-probe experiments we observe that the energy transfer rate increases upon increase of the sample temperature [3]. This temperature dependence can only be simulated with an extended Förster model [4] that includes low wavenumber ground state vibrations and more importantly structural and electronic deformations induced by solvent fluctuations.…”

Section: Fret In Dyads With Orthogonal Transition Moments: Violation mentioning

confidence: 92%

New perspectives on ultrafast Förster Resonant Energy Transfer

Pugliesi

Langhals²,

Kauffmann

et al. 2013

EPJ Web of Conferences

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Abstract. We show that perylene diimide dyads based on a donor-spacer-acceptor motif violate Förster's dipole-dipole interaction picture for energy transfer in the low picosecond to sub-100 femtosecond regime. First theoretical explanations are presented. Perylene bisimide dyads reveal new energy transfer mechanismsWe present an in-depth investigation of the very principles of Förster Resonant Energy Transfer (FRET) by pump-probe and 2D electronic spectroscopy, chemical variation and ab initio calculations on an extended set of perylene diimide dyads based on a donor-spacer-acceptor motif (as shown in figure 1 and 2). These dyads have revealed many unexpected deviations from the behaviour predicted by the simple dipole-dipole interaction picture used to describe FRET. These surprising results range from unexpectedly fast FRET rates going far below 400 fs to picosecond energy transfer in dyads with orthogonal transition dipoles and deviations from the 1/R 6 donor-acceptor distance dependence. For dyads with electron donating spacers that quench the fluorescence of the energy donor, the electron transfer transition itself mediates FRET.FRET has become a process of ubiquitous importance in chemistry and biochemistry. While proximity measurements of light absorbing and fluorescent structures still rely on the basic theory of FRET, our results show that a more refined model is required for an accurate description of this photophysical process. Ultrafast FRET in dyads with parallel transition moments: strong electronic and vibrational mixingTransient absorption measurements of the perylene-terylene diimide dyad with parallel transition dipole moments shown in figure 1 (middle) have been carried out with the pump-probe setup described in ref [1]. The spectral changes in the NIR, where donor and acceptor have distinct absorption bands at 820 and 880 nm (see figure 1b), reveal an ultrafast energy transfer below 400 fs. To further elucidate the mechanism behind this ultrafast FRET, 2D electronic spectra were recorded with the setup described in ref [2]. The 2D spectrum in figure 1c reveals that the onset of the stimulated emission occurs for as early a waiting time as 30 fs (see figure 1c, white arrow) and 2D spectra recorded at longer waiting times indicate that the FRET is as fast as 50 fs. While in the pump-probe experiments the NOPA pulse used for excitation only covers the highest vibronic band This is an Open Access article distributed under the terms of the Creative Commons Attribution License 2.0, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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Förster Resonant Energy Transfer in Orthogonally Arranged Chromophores

Cited by 107 publications

References 31 publications

A Concept for Molecular Addressing by Means of Far-reaching Electromagnetic Interactions in the Visible

A Concept for Molecular Addressing by Means of Far-reaching Electromagnetic Interactions in the Visible

Ultrafast Electronic Energy Transfer Beyond the Weak Coupling Limit in a Proximal but Orthogonal Molecular Dyad

New perspectives on ultrafast Förster Resonant Energy Transfer

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