Centro de Investigaciones Químicas, IICBA, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Col. Chamilpa, Cuernavaca, Morelos, 62209, (México).
Chemphyschem. 2023 Jun 15;24(12):e202300071. doi: 10.1002/cphc.202300071. Epub 2023 Apr 26.
In a one-step reaction, we prepared a dibenzylamine perylene diimide derivative (PDI). Its double hook structure allows for self-association with a constant of K ∼10 M determined by fluorescence. We confirmed its ability to bind PAHs using UV/Vis, fluorescence, and H NMR titrations in CHCl . The complex formation signature in UV/vis is a new band at 567 nm. The calculated binding constants (K ∼10 M ) follow the trend pyrene>perylene>phenanthrene>naphthalene>anthracene. Theoretical modeling of these systems using DFT ωB97X-D/6-311G(d,p) proved helpful in rationalizing the complex formation and the observed association trend. The distinctive signal in UV/vis is due to a charge transfer in the complex from orbitals in the guest to the host. SAPT(DFT) confirmed that the driving forces in the complex formation are exchange and dispersion (π-π interactions). Still, the recognition ability depends on the electrostatic component of the interaction, a minor fraction.
在一步反应中，我们制备了二苄基胺苝二酰亚胺衍生物（PDI）。其双钩结构允许通过荧光确定的常数 K∼10 M 进行自缔合。我们通过 UV/Vis、荧光和 H NMR 滴定在 CHCl3 中证实了其与 PAHs 结合的能力。在 UV/vis 中，复合物形成的特征是在 567nm 处出现新的带。计算得到的结合常数（K∼10 M）遵循以下趋势：芘>苝>菲>萘>蒽。使用 DFT ωB97X-D/6-311G(d,p)对这些体系进行理论建模有助于合理化复合物的形成和观察到的缔合趋势。在 UV/vis 中观察到的独特信号是由于客体分子轨道到主体分子轨道的电荷转移导致复合物形成。SAPT（DFT）证实，复合物形成的驱动力是交换和色散（π-π 相互作用）。尽管如此，识别能力取决于相互作用的静电分量，这只是一小部分。
