C50B54_C88B78_B184-Zhang-Min-2022-Scientific_Reports

 Boron and boron‑based nanoclusters exhibit unique structural and bonding patterns in chemistry. Extensive density functional theory calculations performed in this work predict the mononuclear  walnut‑like C i C50B54 (1) (C 2B10 @C 48B44 ), C1 C50B54 (2) (CB 11 @C 49B43 ), and S10 C50B54 (3) (B 12 @C 50B42 )  which contain one icosahedral‑CnB12‑n core (n = 0, 1, 2) at the center following the Wade’s skeletal  electron counting rules and the approximately electron sufficient binuclear peanut‑like C s C88B78 (4) ((C 2B10 ) 2 @C 84B58 ), C s C88B78 (5) ((CB 11 ) 2 @C 86B56 ), C s C88B78 (6) ((B 12 ) 2 @C 88B54 ), C s B180 (7) ((B 12 ) 2@B156 ), C s B182 (8) ((B 12 ) 2@B158 ), and C s B184 (9) ((B 12 ) 2@B160 ) which encapsulate two interconnected CnB12‑n  icosahedrons inside. These novel core–shell borafullerene and borospherene nanoclusters appear to  be the most stable species in thermodynamics in the corresponding cluster size ranges reported to  date. Detailed bonding analyses indicate that the icosahedral B 122− , CB 11− , and C 2B10 cores in these  core–shell structures possess the superatomic electronic configuration of 1S 2 1P 6 1D 10 1F 8 , rendering  spherical aromaticity and extra stability to the systems. Such superatomic icosahedral‑CnB12‑n stuffed  borafullerenes and borospherenes with spherical aromaticity may serve as embryos to form bulk  boron allotropes and their carbon‑boron binary counterparts in bottom‑up approaches.