Departamento de Química Física, Facultade de Ciencias, Universidade de Santiago de Compostela, Campus de Lugo, Avda. Alfonso X El Sabio s/n, 27002 Lugo, Galicia, Spain.
Phys Chem Chem Phys. 2012 Jan 7;14(1):104-12. doi: 10.1039/c1cp22823d. Epub 2011 Nov 8.
Complexes formed by anions and substituted molecular bowls were studied by means of computational methods. The bowls consisted of corannulene molecules substituted with five or ten F, Cl, or CN groups, whereas Cl(-), Br(-) and BF(4)(-) were the anions considered. Substitution with F, Cl and CN hardly affects the geometry of the bowl, but produces an inversion of the molecular electrostatic potential of the bowls, which becomes positive over the two faces of the bowl, therefore interacting favorably with anions. In all cases considered, the most stable complex presents the anion interacting with the concave side of the bowl. The strength of the interaction roughly follows the values of molecular electrostatic potential, being more stable as more positive is the potential. The preference of anions to interact with the concave side of the bowls has its origin in stronger electrostatic and dispersion interactions. Though the solvent produces an important decrease in the stability of the complexes, the results suggest the possibility of employing these substituted buckybowls as anion receptors with a preferential concave complexation, especially for large anions.
采用计算方法研究了阴离子和取代分子碗形成的配合物。碗由用五个或十个 F、Cl 或 CN 基团取代的[5]轮烯分子组成，而 Cl(-)、Br(-) 和 BF(4)(-)是考虑的阴离子。用 F、Cl 和 CN 取代几乎不影响碗的几何形状，但会使碗的分子静电势反转，使碗的两个面变成正的，因此与阴离子有利相互作用。在所考虑的所有情况下，最稳定的配合物呈现出与碗的凹面相互作用的阴离子。相互作用的强度大致遵循分子静电势的值，静电势越正，配合物越稳定。阴离子优先与碗的凹面相互作用的原因在于更强的静电和色散相互作用。尽管溶剂会使配合物的稳定性大大降低，但结果表明，这些取代的 buckybowls 有可能作为阴离子受体，具有优先的凹面配位，特别是对大的阴离子。
