Theoretical investigation of electronic excitation energy transfer in bichromophoric assemblies

Fückel, Burkhard; Köhn, Andreas; Harding, Michael E.; Diezemann, Gregor; Hinze, G.; Basché, Thomas; Gauß, Jürgen

doi:10.1063/1.2829531

Cited by 90 publications

(129 citation statements)

References 57 publications

(99 reference statements)

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“…It is interesting to mention here the theoretical investigations of PDI and TDI based diads by Fückel et al and Beljonne et al where PDI and TDI act as donor and acceptor, respectively. [65,66] Significant discrepancies between theoretical and experimental values were found, with the theory underestimating the transfer rates by a factor of 10 for donor-acceptor distances shorter than 50 and certain relative orientations. The polarizability of the bridges was found responsible for the deviating values, leading to an enhancement of these interchromophore interactions.…”

Section: Wwwchemphyschemorgmentioning

confidence: 89%

Energy Transfer Pathways in a Rylene‐Based Triad

et al. 2010

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Herein, a study on the excitation energy migration is reported for a newly synthesized Triad with a well-defined architecture consisting of a central terrylenediimide decorated with four perylenediimide and sixteen naphthalenemonoimide chromophores. Steady-state femto- and picosecond time-resolved spectroscopy were employed to unveil the excited states dynamics in solution. Compared with the results obtained from the corresponding model compounds, the Triad is an efficient light collector over the entire visible spectral range and the fluorescence occurs mostly from the core with a quantum yield as high as 60%. The results suggest that selective excitation of the naphthalenemonoimide chromophores results in an efficient energy transfer that occurs in a cascade fashion (through the perylenediimide chromophores) towards the terrylenediimide core with time constants of <200 fs and 3.7 ps. Naphthalenemonoimide chromophores can also transfer their excitation energy to the terrylenediimide core directly via two parallel pathways with time constants of 1.5 and 8.4 ps, respectively. Additionally, single-molecule confocal microscopy experiments revealed strong emission from the terrylenediimide unit upon excitation of the naphthalenemonoimide chromophores. As time evolved, stepwise photobleaching of the multichromophoric Triad single molecules embedded in a PMMA polymer film was observed, resulting in a 96 percent probability of observing perylenediimide emission before final photobleaching under ambient conditions, substantiating the cascade energy transfer pathway. Under nitrogen atmosphere however, no perylenediimide emission could be observed for single Triad molecules embedded in a PMMA polymer film, likely as a result of the prolonged photostability of the terrylenediimide core in absence of oxygen.

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Section: Wwwchemphyschemorgmentioning

confidence: 89%

Energy Transfer Pathways in a Rylene‐Based Triad

et al. 2010

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“…While the first problem has been tackled in the last decade with high precision mainly due to advances in molecular electronic structure calculations (see refs. [12][13][14][15]) a satisfactory ab initio computation of what is known from Fçrster's theory as the frequency overlap (here represented by D EET ) is missing.…”

Section: Introductionmentioning

confidence: 98%

A Mixed Quantum–Classical Description of Excitation Energy Transfer in Supramolecular Complexes: Förster Theory and beyond

et al. 2011

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Electronic excitation energy transfer (EET) is described theoretically for the chromophore complex P(4) formed by a butanediamine dendrimer to which four pheophorbide-a molecules are covalently linked. To achieve a description with atomic resolution, and to account for the effect of an ethanol solvent, a mixed quantum-classical methodology is utilized. Room-temperature molecular dynamics simulations are used to describe the nuclear dynamics, and EET is accounted for in utilizing a mixed quantum-classical formulation of the transition rates. Therefore, the full quantum expression of the EET rates is given and the change to a mixed quantum-classical version is briefly explained. The description results in the calculation of transition rates which coincide rather satisfactory with available experimental data on P(4). It is also shown that different assumptions of classical Förster theory are not valid for P(4). The temporal behavior of EET deduced from the rate equations is confronted with that following from the solution of the time-dependent Schrödinger equation entering the mixed quantum-classical description of EET. From this we can conclude that EET in flexible chromophore complexes such as P(4) can be rather satisfactory estimated by single transition rates. A correct description, however, is only achievable by using a sufficiently large set of rates that correspond to the various possible equilibrium configurations of the complex.

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“…The literature on the calculation of the electronic coupling is voluminous [1][2][3][4][5][6][7][8][9][10][16][17][18][19][20][21][22][23][24][25][26]. However, most of them are focused on singlet-to-singlet (S-S) energy transfer, wherein energy is exchanged between two molecular moieties that have singlet spin multiplicities.…”

Section: Introductionmentioning

confidence: 99%

“…Nonradiative excitation energy transfer (EET) from a donor to an acceptor chromophore is a fundamental process in photochemically active systems [1][2][3][4][5][6][7][8], such as light-harvesting antenna [2,3] and the complexes of green photosynthetic bacterium [4,5] in the natural world. Furthermore, there has been an escalation in the number of diverse and novel synthetic systems that utilize EET.…”

Section: Introductionmentioning

confidence: 99%