LECIME, Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (CNRS UMR-7575), Ecole Nationale Supérieure de Chimie de Paris-Chimie ParisTech, 11, rue Pierre et Marie Curie, F-75231 Paris Cedex 05, France.
J Phys Chem A. 2010 Aug 19;114(32):8434-43. doi: 10.1021/jp104439q.
With the aim of getting insights into the peculiar electronic, structural, and photophysical properties of four expanded pyridinium systems of potential use as electron acceptors in supramolecular architectures, their electronic and geometrical structures, at both the ground and the excited states, were investigated by the means of density functional theory (DFT) and time-dependent DFT (TD-DFT). Solvent effects were included by the means of a polarizable continuum model (PCM) at both the ground and the excited states. In particular, the computed photophysical behaviors (absorption and emission) of the fused architectures were compared to those of the respective branched precursors in order to clarify the origin(s) of (i) the extension of their electronic absorption toward the visible region and (ii) the increase of their luminescence quantum yields and red-shifted emission wavelengths experimentally observed. The theoretical insights gained allow for a clear-cut explanation of the different behavior of these systems of interest as electron acceptors and luminophores for more complex supramolecular architectures and opens the route for a joint experimental and theoretical design of new pyridinium-based acceptors.
为了深入了解四个具有扩展吡啶鎓结构的体系在超分子架构中作为电子受体的特殊电子、结构和光物理性质，我们采用密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）研究了它们在基态和激发态下的电子和几何结构。通过在基态和激发态下使用极化连续模型（PCM）来考虑溶剂效应。特别是，我们将融合架构的计算光物理行为（吸收和发射）与各自的支化前体进行了比较，以阐明（i）它们的电子吸收向可见光区域的扩展和（ii）实验观察到的发光量子产率和红移发射波长增加的原因。所获得的理论见解为这些作为电子受体和发光体的感兴趣体系在更复杂的超分子架构中的不同行为提供了清晰的解释，并为新的基于吡啶鎓的受体的联合实验和理论设计开辟了道路。
