Predicting lanthanide boride inverse sandwich tubular molecular rotors with the smallest core–shell structure

Abstract

Extensive first-principles theory calculations predict the possibility of bi-decker inverse sandwich complexes La2[B18], La2[B18]2−, and La2[B2@B18], with the B2-centered La2[B2@B18] as a tubular molecular rotor possessing the smallest core–shell structure.

From inverse sandwich Ta2B7+ and Ta2B8 to spherical trihedral Ta3B12−: prediction of the smallest metallo-borospherene

“…PE measurements and infrared photodissociation (IR-PD) spectra in combination with rst-principles theory calculations have proven to be powerful approaches in characterizing novel clusters in gas phases. [3][4][5][6][7][17][18][19][20][21][22][23][24][25][26][27][28]62 As shown in Fig. 4, the highsymmetry Ta 3 B 12 À (3) exhibits relatively simple IR and Raman spectral patterns, with the major IR active peaks at 507 (e 0 ), 559 (e 0 ), 668 ða 00 2 Þ, and 881 (e 0 ) cm À1 (Fig.…”

Perfect cubic La-doped boron clusters La6&[La@B24]+/0as the embryos of low-dimensional lanthanide boride nanomaterials

“…Persistent joint photoelectron spectroscopy (PES) and rstprinciples theory investigations in the past two decades by Wang and coworkers have unveiled an unexpectedly rich landscape for size-selected boron clusters from planar or quasiplanar B n À/0 (n ¼ 3-38, 41 and 42) to cage-like borospherenes @B 18 ] which possesses the smallest core-shell structure reported in boron clusters. 26 Bulk lanthanide hexaboride LaB 6 (7) has been widely used as cathode materials due to its numerous excellent properties such as low work function, ultrahigh hardness, high chemical inertness, and high melting point. [27][28][29][30] It possesses a typical cubic CaB 6 -type lattice (Pm 3m, O h 1 ) characterized with a 3D network constituted of B 6 octahedrons, with the interstitial locations lled by trivalent La atoms.…”

Donor–acceptor duality of the transition-metal-like B2 core in core–shell-like metallo-borospherenes La3&[B2@B17]− and La3&[B2@B18]−

“…The donor-acceptor duality of the transition-metal-like B 2 core plays an essential role in stabilizing these novel complexes, in particular, its strong p-donation to the three equivalent La atoms in equatorial directions makes major contributions to the overall orbital interaction. Initial results indicate that the experimentally observed spherical trihedral D 3h Tb 3 68 It is anticipated that more B n units with donor-acceptor dualities could exist in 3D complexes or low-dimensional nanostructures which may have important applications in materials science, molecular devices, and chemical catalysis.…”