Finding all‐nonmetal transition‐metal‐like superatom and its magnetic building block

Abstract

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 Al 13 with 2P 5 sub shell (corresponding to the 3p 5 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 B 6 cluster with characteristic jellium electron configuration 1S 2 1P 6 2S 2 1D 8 in the triplet ground state can mimic the behaviors of transitionmetal Ni atom with electron configuration 3s 2 3p 6 4s 2 3d 8 in electronic configuration, physics and chemistry. Interestingly, the characteristic order of 1S1P2S1D for the B 6 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 B 6 with the spin moment value of 2l B is a new all-nonmetal transition-metal nickel-like superatom exhibiting a new kind of allnonmetal magnetic superatom. Finding the application of the all-nonmetal magnetic superatom, we encapsulate the magnetic superatom B 6 inside fully hydrogenated fullerene forming a clathrate B 6 @C 60 H 60 with the spin moment value of 2l B . As the C 60 H 60 cage as a polymerization unit can conserve the spin moment of endohedral B 6 , the clathrate B 6 @C 60 H 60 is a new all-nonmetal magnetic superatom building block. Naturally, magnetic superatom structures of the B 6 and B 6 @C 60 H 60 may be metastable. K E Y W O R D S all-nonmetal magnetic superatom, all-nonmetal octahedral cluster, clathrate B 6 @C 60 H 60 , spin moment, transition-metal Int J Quantum Chem. 2018;118:e25570.