Theoretical Study Of All-nonmetal Transition-metal-like Superatom

In novel superatom chemistry,it is very attractive that all-metal clusters can mimic the behaviors of nonmetal atoms and simple nonmetal molecules.Wizardly all-metal halogen-like superatom Al13 with 2P5 sub shell(corresponding to the 3p5 of chlorine)is the most typical example.In contrast,how to mimic the behaviors of magnetic transition-metal atom using all-nonmetal cluster is an intriguing challenge for superatom chemistry.In response to this based on human intuition,using quantum chemistry methods and extending Jellium model from metal cluster to all-nonmetal cluster,we have found out that all-nonmetal octahedral B6 cluster with characteristic Jellium electron configuration 1S21P62S21D8 in the triplet ground state can mimic the behaviors of transition-metal Ni atom with electron configuration 3s23p64s23d8 in electronic configuration,physics and chemistry.Interestingly,the characteristic order of 1S1P2S1 D for the B6 nonmetal cluster with short B-B lengths is different from that of the traditional Jellium model—1S1P1D2S for metal clusters with long M-M lengths,which exhibits a novel size effect of nonmetal cluster on Jellium orbital ordering.Based on the Jellium electron configuration,the B6 with the spin moment value of 2?B is a new all-nonmetal transition-metal nickel-like superatom exhibiting a new kind of all-nonmetal magnetic superatom.Finding the application of the all-nonmetal magnetic superatom,we encapsulate the magnetic superatom B6 inside fully hydrogenated fullerene forming a clathrate B6@C60H60 with the spin moment value of 2?B.As the C60H60 cage as a polymerization unit can conserve the spin moment of endohedral B6,the clathrate B6@C60H60 is a new all-nonmetal magnetic superatom building block.