skip to main content


Title: Spherical trihedral metallo-borospherenes
Abstract

The discovery of borospherenes unveiled the capacity of boron to form fullerene-like cage structures. While fullerenes are known to entrap metal atoms to form endohedral metallofullerenes, few metal atoms have been observed to be part of the fullerene cages. Here we report the observation of a class of remarkable metallo-borospherenes, where metal atoms are integral parts of the cage surface. We have produced La3B18and Tb3B18and probed their structures and bonding using photoelectron spectroscopy and theoretical calculations. Global minimum searches revealed that the most stable structures of Ln3B18are hollow cages withD3hsymmetry. The B18-framework in the Ln3B18cages can be viewed as consisting of two triangular B6motifs connected by three B2units, forming three shared B10rings which are coordinated to the three Ln atoms on the cage surface. These metallo-borospherenes represent a new class of unusual geometry that has not been observed in chemistry heretofore.

 
more » « less
Award ID(s):
1763380
NSF-PAR ID:
10157952
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
Nature Communications
Volume:
11
Issue:
1
ISSN:
2041-1723
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Because of their interesting structures and bonding and potentials as motifs for new nanomaterials, size-selected boron clusters have received tremendous interest in recent years. In particular, boron cluster anions (B n − ) have allowed systematic joint photoelectron spectroscopy and theoretical studies, revealing predominantly two-dimensional structures. The discovery of the planar B 36 cluster with a central hexagonal vacancy provided the first experimental evidence of the viability of 2D borons, giving rise to the concept of borophene. The finding of the B 40 cage cluster unveiled the existence of fullerene-like boron clusters (borospherenes). Metal-doping can significantly extend the structural and bonding repertoire of boron clusters. Main-group metals interact with boron through s/p orbitals, resulting in either half-sandwich-type structures or substitutional structures. Transition metals are more versatile in bonding with boron, forming a variety of structures including half-sandwich structures, metal-centered boron rings, and metal-centered boron drums. Transition metal atoms have also been found to be able to be doped into the plane of 2D boron clusters, suggesting the possibility of metalloborophenes. Early studies of di-metal-doped boron clusters focused on gold, revealing ladder-like boron structures with terminal gold atoms. Recent observations of highly symmetric Ta 2 B 6 − and Ln 2 B n − ( n = 7–9) clusters have established a family of inverse sandwich structures with monocyclic boron rings stabilized by two metal atoms. The study of size-selected boron and doped-boron clusters is a burgeoning field of research. Further investigations will continue to reveal more interesting structures and novel chemical bonding, paving the foundation for new boron-based chemical compounds and nanomaterials. 
    more » « less
  2. Abstract

    Actinide diatomic molecules are ideal models to study elusive actinide multiple bonds, but most of these diatomic molecules have so far only been studied in solid inert gas matrices. Herein, we report a charged U≡N diatomic species captured in fullerene cages and stabilized by the U-fullerene coordination interaction. Two diatomic clusterfullerenes, viz. UN@Cs(6)-C82and UN@C2(5)-C82, were successfully synthesized and characterized. Crystallographic analysis reveals U-N bond lengths of 1.760(7) and 1.760(20) Å in UN@Cs(6)-C82and UN@C2(5)-C82. Moreover, U≡N was found to be immobilized and coordinated to the fullerene cages at 100 K but it rotates inside the cage at 273 K. Quantum-chemical calculations show a (UN)2+@(C82)2−electronic structure with formal +5 oxidation state (f1) of U and unambiguously demonstrate the presence of a U≡N bond in the clusterfullerenes. This study constitutes an approach to stabilize fundamentally important actinide multiply bonded species.

     
    more » « less
  3. Abstract

    Calcium germanides with two mid‐late rare‐earth metals, Ca5−xGdxGe3and Ca5−xTbxGe3(x≈0.1−0.2), have been synthesized and structurally characterized. Additionally, a lanthanum‐rich germanide with calcium substitutions, La5−xCaxGe3(x≈0.5) has also been identified. The three structures have been established from single‐crystal X‐ray diffraction methods and confirmed to crystallize with the Cr5B3‐type in the tetragonal space groupI4/mcm(no. 140;Z=4; Pearson symboltI32), where part of the germanium atoms are interconnected into Ge2‐dimers, formally [Ge2]6−. Rare‐earth metal and calcium atoms are arranged in distorted trigonal prisms, square‐antiprisms and cubes, centered by Ge or rare‐earth/calcium metal atoms. These studies show that the amount of trivalent rare‐earth metal atoms substituting divalent calcium atoms is in direct correlation with the lengths of the Ge−Ge bond within the Ge2‐dimers, with distance varying between 2.58 Å in Ca5−xGdxGe3and 2.75 Å in La5−xCaxGe3. Such an elongation of the Ge−Ge bond is consistent with the notion that the parent Ca5Ge3Zintl phase (e. g. (Ca2+)5[Ge2]6−[Ge4−]) is being driven out of the ideal valence electron count and further reduced. In this context, this work demonstrates the ability of the germanides with the Cr5B3structure type to accommodate substitutions and wider valence electron count while maintaining their global structural integrity.

     
    more » « less
  4. Abstract

    Unsupported non-bridged uranium–carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizingIh(7)-C80fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@Ih(7)-C80. This endohedral fullerene was prepared utilizing the Krätschmer–Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (NiII-OEP) to produce UCU@Ih(7)-C80·[NiII-OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium–carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@Ih(7)-C80and the covalent nature of the U(f1)=C double bonds were further affirmed through various spectroscopic and theoretical analyses.

     
    more » « less
  5. Abstract

    We present candidate structures for the most stable isomers for the VSc2N@C70, VSc2N@C76, VSc2N@C78, and VSc2N@C80using a systematic procedure that involves all possible isomers of the host fullerene cages. Subsequently, a detailed investigation of structural and electronic properties of the lowest energy isomers is performed using density functional theory in combination with large polarized Gaussian basis sets. The search correctly identifies the experimentally observed VSc2N@C80isomer as the most stable structure. The structural analysis shows that only VSc2N@C70has a non‐IPR cage among the four endohedral fullerenes. Respectively, VSc2N@C70and VSc2N@C76have nearly degenerate spin states with total spinS= 0 andS= 1. All the lowest energy cages are energetically stable and show significant electron accepting capacity comparable to C60.

     
    more » « less