The inner-induced effects of YCN in C76 on the structures and nonlinear optical properties

Abstract

Very recently, an unprecedented novel monometallic cluster of fullerenes entrapping a yttrium cyanide (YCN) cluster inside a popular C82 cage YCN@Cs(6)-C82 was synthesized and characterized. Inspired by this investigation, four non-IPR YCN@C1(17459)-C76, YCN@C2v(19138)-C76, YCN@C2(17646)-C76, and YCN@C1(17894)-C76 (1, 2, 3, and 4) containing a pair of adjacent pentagons are designed to explore the encapsulated molecular effect on their interaction energies and nonlinear optical properties. The interaction energy (E int) values of 1, 2, 3, and 4 are -481.35 (1), -477.91 (2), -482.04 (3), -482.69 (4) kcal mol(-1), respectively, which shows that the E int value of 4 is the largest. Furthermore, the electron-transfer is mainly from the YCN to C76 cage. When YCN is encapsulated into C76 cage, we can find that the α0 values of the four molecules are very close, ranging from 6.50 × 10(2) to 6.65 × 10(2) au. Significantly, the first hyperpolarizabilities are in relation to the encapsulated molecular: 1.63 × 10(3) (1) > 8.03 × 10(2) (2) > 7.76 × 10(2) (4) > 4.86 × 10(2) au (3), the results show that the βtot value of 1 is the largest. Besides this, the encapsulation of the YCN to C76 cage brings some distinctive changes in its UV-vis spectra along with its other electronic properties that might be used by the experimentalists to develop the potential nonlinear optical nanomaterials based on endohedral metallofullerenes.

Undiscovered Effect of C↔N Interchange Inside the Metal Carbonitride Clusterfullerenes: A Density Functional Theory Investigation

“…On the other hand, several systematic theoretical studies have been performed regarding the carbonitride ECFs. − However, most of them only focused on searching new parent cages to encapsulate the metal clusters without taking the internal NC orientation into account. In 2010, we first predicted the possible structures of Sc 3 CN@C 2 n (2 n = 68, 78, and 80) and found that they all energetically prefer C rather than N at the cluster center, which is in sharp contrast to the classical N-centered nitride ECFs. , Recently, similar computational results were obtained by Zhang et al., who further found that MNC@C 76 (M = Sc, Y), however, slightly favor the N atom at the cluster center instead of C. They rationalized the difference simply by the charge state of the CN unit: (CN) − and (CN) 3– feature more negative charges on the N and C atoms, respectively, which thus reside at the cluster center to coordinate with the metal cation(s).…”