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Diels-Alder Cycloaddition on Non-Isolated-Pentagon-Rule C2v(19138)-C76 and YNC@C2v(19138)-C76: The Difference in Regioselectivity Caused by the Inner Metallic Cluster.

Diels-Alder reactions of cyclopentadiene to C2v(19138)-C76 and YNC@C2v(19138)-C76 violating the isolated pentagon rule (IPR) have been systematically studied by means of density functional theory calculations. As for the free fullerene, the [5,5]-bond of type-E in the adjacent pentagon pair is the most favorable from thermodynamic and kinetic viewpoints, which is attributed to the highly strained carbon atoms accompanied by the suitable LUMO shape with large distribution to interact with cyclopentadiene. Upon encapsulating the YNC cluster, the corannulene-type bond s-s and the pyracylene-type bond v-u become the two most reactive addition sites under thermodynamic and kinetic conditions, which possess similar reaction energies and energy barriers. Especially, bond s-s exhibits the larger reaction energy and the lower energy barrier than that on the free fullerene, which should be ascribed to the shorter bond length and larger POAV value of bond s-s after trapping the metallic cluster. The suitable unoccupied molecular orbital lobes with large distributions on bonds s-s and v-u are also an advantage of cycloadditions. This work presents the first example that the most favorable addition site is remote from the adjacent pentagon pair in the fullerene cage after encapsulating a metallic cluster.