The V-shaped polar molecules encapsulated into Cs (10528)-C72: stability and nonlinear optical response

Recently, a new sulfide cluster fullerene, Sc2S@Cs (10528)-C72 containing two pairs of fused pentagons has been isolated and characterized (Chen et al., J. Am. Chem. Soc., 2012, 134, 7851). Inspired by this investigation, we propose a question: what properties will be influenced by the interaction between the encapsulated V-shaped polar molecule and C72? To answer this question, four encapsulated metallic fullerenes (EMFs) M2N@C72 (M = Sc or Y, N = S or O) along with pristine Cs-C72 (10528) were investigated by quantum chemistry methods. The results show that the Egap (3.01-3.14 eV) of M2N@C72 are significantly greater than that of pristine Cs-C72 (10528) (2.34 eV). This indicates that the stabilities of these EMFs increase by encapsulating the V-shaped polar molecule into the fullerene. Furthermore, the natural bond orbital (NBO) charge analysis indicates electron transfer from M2N to C72 cage, which plays a crucial role in enhancing first hyperpolarizability (βtot). The βtot follows the order of 1174 au (Y2O@C72) ≈ 1179 au (Sc2O@C72) > 886 au (Y2S@C72) ≈ 864 au (Sc2S@C72) > 355 au (C72). This indicates that the βtot of M2N@C72 is more remarkable than that of pristine Cs-C72 (10528) due to the induction effect of the encapsulated molecule. Compared with sulfide cluster fullerenes (Y2S@C72 and Sc2S@C72), oxide cluster fullerenes (Sc2O@C72 and Y2O@C72) show much larger βtot due to the small ionic radius and the large electronegativity of oxygen. In contrast, the metal element (scandium and yttrium) has a slight influence on the βtot. Thus, oxide cluster fullerenes are candidates to become promising nonlinear optical materials with higher performance.