Abstract
Cage-like and core-shell metallo-borospherenes exhibit interesting structures and bonding. Based on extensive global searches and first-principles theory calculations, we predict herein the perfect tetrahedral cage-like Td La4B24 (1) and core-shell Td La4B29 (2), Td La4B29+ (3), and Td La4B29- (4) which all possess the same geometrical symmetry as their carbon fullerene counterpart Td C28, with four equivalent interconnected B6 triangles on the cage surface and four nona-coordinate La centers in four conjoined η9-B9 rings. In these tetra-La-doped boron complexes, La4[B@B4@B24]0/+/- (2/3/4) in the structural motif of 1 + 4 + 28 contain a B-centered tetrahedral Td B@B4 core in a La-decorated tetrahedral La4B24 shell, with the negatively charged tetra-coordinate B- at the center being the boron analog of tetrahedral C in Td CH4 (B- ~ C). Detailed orbital and bonding analyses indicate that these Td lanthanide boride complexes are spherically aromatic in nature with a universal La--B9 (d-p) σ and (d-p) δ coordination bonding pattern. The IR, Raman, and UV-Vis or photoelectron spectra of these novel metallo-borospherenes are computationally simulated to facilitate their spectral characterizations. Graphical abstract.
Highlights
Boron as a prototypical electron-deficient element possesses a rich chemistry only to carbon in the periodical table
Joint ion-mobility measurements and density functional theory (DFT) investigations indicated that boron cluster monocations (Bn+) possess double-ring tubular geometries in the size range between n = 16–25 [12]
Extensive global minimum (GM) searches showed that complicated structural competitions exist in medium-sized Bn clusters, with B46 being the smallest core-shell boron cluster (B4@B42) and B48, B54, B60, and B62 being the first bilayer boron clusters predicted to date [13, 14]
Summary
Boron as a prototypical electron-deficient element possesses a rich chemistry only to carbon in the periodical table. Persistent joint photoelectron spectroscopy (PES) and first-principles theory investigations in the past two decades have unveiled a rich landscape for sizeselected boron clusters (Bn−/0) from planar or quasi-planar structures (n = 3–38, 41, 42) to cage-like borospherenes (C3/C2 B39− and D2d B40−/0 ) which are all characterized with delocalized multi-center bonding [2,3,4,5,6]. Endohedral M@B40 (M = Ca, Sr) and exohedral M&B40 (M = Be, Mg) metallo-borospherenes were predicted in theory shortly after the discovery of D2d B40−/0 [9]. Joint ion-mobility measurements and density functional theory (DFT) investigations indicated that boron cluster monocations (Bn+) possess double-ring tubular geometries in the size range between n = 16–25 [12]. Extensive GM searches showed that complicated structural competitions exist in medium-sized Bn clusters, with B46 being the smallest core-shell boron cluster (B4@B42) and B48, B54, B60, and B62 being the first bilayer boron clusters predicted to date [13, 14]
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
