Superatomic icosahedral-CnB12-n (n=0, 1, 2) Stuffed mononuclear and binuclear borafullerene and borospherene nanoclusters with spherical aromaticity

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) (C2B10@C48B44), C-1 C50B54 (2) (CB11@C49B43), and S-10 C50B54 (3) (B-12@C50B42) 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) ((C2B10)(2)@C84B58), C-s C88B78 (5) ((CB11)(2)@C86B56), C-s C88B78 (6) ((B-12)(2)@C88B54), C-s B-180 (7) ((B-12)(2)@B-156), C-s B-182 (8) ((B-12)(2)@B-158), and C-s B-184 (9) ((B-12)(2)@B-160) 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-12(2-), CB11-, and C2B10 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.

Automated summary

Boron and boron-based nanoclusters exhibit unique structural and bonding patterns, including core-shell borafullerene and borospherene nanoclusters. These clusters possess superatomic electronic configurations and spherical aromaticity, resulting in extra stability.