Fully inorganic (carbon-free) fullerenes? The boron-nitrogen case

Silaghi‐Dumitrescu, Ioan; Haiduc, Ionel; Sowerby, D. Bryan

doi:10.1021/ic00069a034

Cited by 58 publications

(28 citation statements)

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“…Analogous to carbon fullerenes, BN cages composed of squares, hexagons, and octagons with alternate B–N arrangement were theoretically predicted by semiempirical and ab initio calculations. − In 1998, Bando’s group , reported experimental observation of single layered and nested BN fullerenes with rectangle-like shapes from HREM images. The smallest and most observed BN cages fall in a diameter range of 0.4 nm to 0.7 nm, corresponding to the B 12 N 12 , B 16 N 16 , and B 28 N 28 octahedral polyhedra from theoretical predictions.…”

Section: Endohedrally Doped Cages Of Compoundsmentioning

confidence: 99%

Endohedrally Doped Cage Clusters

2020

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The discovery of carbon fullerene cages and their solids opened a new avenue to build materials from stable cage clusters as “artificial atoms” or “superatoms” instead of atoms. However, cage clusters of other elements are generally not stable. In 2001, ab initio calculations showed that endohedral doping of Zr and Ti atoms leads to highly stable Zr@Si16 fullerene and Ti@Si16 Frank–Kasper polyhedral clusters with large HOMO–LUMO gaps. In 2002, Zr@Ge16 was shown to form a Frank–Kasper polyhedron, suggesting the possibility of designing novel clusters by tuning endohedral and cage atoms. These results were subsequently confirmed from experiments. In the past nearly two decades, many experimental and theoretical studies have been carried out on different clusters, and many very stable cage clusters with possibly high abundance have been found by endohedral doping. Indeed in 2017, Ta@Si16 and Ti@Si16 cage clusters have been synthesized in bulk quantity of about 100 mg using a dry-chemistry method, giving rise to a new hope of developing cluster-based materials in macroscopic quantity besides the well-known C60 fullerene solid. Also, wet-chemistry methods have been used to synthesize endohedrally doped clusters as well as ligated clusters and their solids, which auger well for the development of novel nanostructured materials using atomically precise clusters with unique properties. In this comprehensive review, we present results of many such developments in this fast-growing field including (i) endohedrally doped Al, Ga, and In clusters, (ii) small endohedral carbon fullerene cages with ≤ 28 carbon atoms, (iii) metal doped boron cages, (iv) endohedrally doped cages of group 14 elements (Si, Ge, Sn, and Pb), (v) coinage metal (Cu, Ag, Au) cages doped with a transition metal atom as well as their ligated clusters and crystals, (vi) endohedrally doped cages of compound semiconductors, and (vii) multilayer Matryoshka cages and core–shell structures. In a large number of cases, we have performed ab initio calculations to present updated results of the most stable atomic structures and fundamental electronic properties of the endohedrally doped cage clusters. We discuss electronic, magnetic, optical, and catalytic properties in order to shed light on their potential applications. The stability of the doped cage clusters has been correlated to the concept of filling the electronic shells for superatoms such as within a spherical potential model and also using various electron counting rules including Wade–Mingos rules, systems with 18 and 32 electrons, and the spherical aromaticity rule. We also discuss cluster–cluster interaction in cluster dimers and assemblies of some of the promising doped cage clusters in different dimensions. Finally, we give a perspective of this field with a bright future.

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Section: Endohedrally Doped Cages Of Compoundsmentioning

confidence: 99%

Endohedrally Doped Cage Clusters

2020

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“…Although the pure carbon forms of buckyballs are known for their stability, replacing each C 2 group with a B–N has been proposed and experimentally known almost since the beginning of fullerene chemistry in the 1980s. − Although such cages have more desirable macroscopic properties such as melting points or sheer strength than their pure carbon cousins, − the stability of the individual cages at the molecular level, that is, the average of the bond strengths, is actually weaker in the boron nitride fullerenes or nanotubes. The dative-type noncovalent interactions between the separate molecules make for more desirable mechanical properties, but the individual boron nitride structures are easier to break.…”

Section: Introductionmentioning

confidence: 99%

Boron-Doped C₂₄ Fullerenes for Alkyl Functionalization or Potential Polymerization

Hurst

Fortenberry

2018

ACS Omega

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Replacing a single carbon atom in C 24 with a boron atom allows the functionalization of one additional carbon atom. Such a process involves little energy cost with regard to the structure of the fullerene. Two such replacements are required if the fullerenes are to act as “pearls on a string”. This work shows trends for increasingly higher levels of carbon replacement with boron as well as hydrogenation, methylation, and ethylation of a subsequent carbon atom in such a boron-doped small fullerene. Additionally, dimers are shown to be stable, and the linking ethyl groups actually stabilize the overall structure more than when the ethyl groups are on the surface of the structure and are not serving as linkers. Such stringed fullerenes would certainly have applications to materials science if polymers could be made from these stringed pearls and would be suitable for neutron radiation shielding in spacecraft or spacesuits.

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“…These authors noted that the N-N-N bond angles in dodecahedral N20 are exactly 1 0 8 O , very close to the tetrahedral bond angle 109. 5', suggesting that N2o may be relatively unstrained. Bliznyuk et ~1 .…”

Section: Introductionmentioning

confidence: 99%

Ab initio theoretical studies on N₂₈, B₄N₂₄, B₁₂N₁₆, and B₁₆N₁₂ with T_d symmetry

Jiang

1996

Chin. J. Chem.

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Structures, energies and vibrational hquencies have been calculated for hollow cage clusters N28, B4N24, B12N16, and B16Nl2 with Td symmetry using ab initw quantum mechanical methods at the RHF/3-21G level. Each species is predicted to be both chemically and kinetically stable. Skeletal polyhedrons of all considered boron nitride hollow cage clusters are constructed from 5 and Smembered rings. KeywordsNitrogen cluster, boron nitride cluster, ab initio molecular orbital theory, fullerene

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Fully inorganic (carbon-free) fullerenes? The boron-nitrogen case

Cited by 58 publications

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Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

Boron-Doped C₂₄ Fullerenes for Alkyl Functionalization or Potential Polymerization

Ab initio theoretical studies on N₂₈, B₄N₂₄, B₁₂N₁₆, and B₁₆N₁₂ with T_d symmetry

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Fully inorganic (carbon-free) fullerenes? The boron-nitrogen case

Cited by 58 publications

References 0 publications

Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

Boron-Doped C24 Fullerenes for Alkyl Functionalization or Potential Polymerization

Ab initio theoretical studies on N28, B4N24, B12N16, and B16N12 with Td symmetry

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Boron-Doped C₂₄ Fullerenes for Alkyl Functionalization or Potential Polymerization

Ab initio theoretical studies on N₂₈, B₄N₂₄, B₁₂N₁₆, and B₁₆N₁₂ with T_d symmetry