Supramolecular organization and charge transport properties of self-assembled π-π stacks of perylene diimide dyes.

Université de Bordeaux, Institut des Sciences Moléculaires, UMR 5255 CNRS, 351 Cours de la Libération, 33405 Talence, France.
The Journal of Physical Chemistry B (Impact Factor: 3.38). 03/2011; 115(18):5593-603. DOI: 10.1021/jp111422v
Source: PubMed

ABSTRACT Molecular dynamics (MD) simulations have been coupled to valence bond/Hartree-Fock (VB/HF) quantum-chemical calculations to evaluate the impact of diagonal and off-diagonal disorder on charge carrier mobilities in self-assembled one-dimensional stacks of a perylene diimide (PDI) derivative. The relative distance and orientation of the PDI cores probed along the MD trajectories translate into fluctuations in site energies and transfer integrals that are calculated at the VB/HF level. The charge carrier mobilities, as obtained from time-of-flight numerical simulations, span several orders of magnitude depending on the relative time scales for charge versus molecular motion. Comparison to experiment suggests that charge transport in the crystal phase is limited by the presence of static defects.

  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: This review describes the photodriven energy- and electron-transfer processes of the columnar perylenediimide (PDI) nanostructures for efficient light-energy conversion by employing the self-assembly models. The charge separation and the directional charge transport of the oligomers, aggregates, and one-dimensional (1D) nanostructures of PDIs have been clarified by using time-resolved transient absorption techniques. Excited states, exciton migration, and excitation energy-transfer processes were examined in the first part. The second part involves the electron hopping, photodriven electron transfer and transport events taking place within the various PDI nanostructures.
    ECS Journal of Solid State Science and Technology. 08/2013; 2(10):M3051.
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: We address the calculation of charge carrier mobility of liquid-crystalline columnar semiconductors, a very promising class of materials in the field of organic electronics. We employ a simple coarse-grained theoretical approach and study in particular the temperature dependence of the mobility of the well-known triphenylene family of compounds, combining a molecular-level simulation for reproducing the structural changes and the Miller-Abrahams model for the evaluation of the transfer rates within the hopping regime. The effects of electric field, positional and energetic disorder are also considered. Simulations predict a low energetic disorder (~0.05 eV), slightly decreasing with temperature within the crystal, columnar and isotropic phases, and fluctuations of the square transfer integral of the order of 0.003 eV(2). The shape of the temperature-dependent mobility curve is however dominated by the variation of the transfer integral and barely affected by the disorder. Overall, this model reproduces semi-quantitatively all the features of experimentally measured mobilities, on one hand reinforcing the correctness of the hopping transport picture and of its interplay with system morphology, and on the other suggesting future applications for off-lattice modeling of organic electronics devices.
    Physical Chemistry Chemical Physics 02/2012; 14(16):5368-75. · 4.20 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Columnar stacks of N,N′-di(2-(trimethylammoniumiodide)ethylene) perylenediimide (TAIPDI)n can host meso-tetrakis(4-sulfonatophenyl)porphyrin zinc tetrapotassium salt (ZnTPPSK4) molecules at different ratios through the ionic and π–π interactions prompted by an aqueous environment. Photoexcitation of this host–guest complex generates very fast charge separation (1.4 × 1012 s–1). Charge recombination is markedly decelerated by a probable electron delocalization mechanism along the long-range of tightly stacked TAIPDIs (4.6 × 108 s–1), giving an exceptional kCS/kCR ratio of 3000 as determined by using time-resolved transient absorption techniques.
    The Journal of Physical Chemistry C 10/2012; 116(44):23274–23282. · 4.84 Impact Factor