Aromaticity of Planar Boron Clusters Confirmed

Aihara, Jun‐ichi; Kanno, Hiroaki; Ishida, Toshimasa

doi:10.1021/ja053171i

Cited by 167 publications

(144 citation statements)

References 76 publications

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“…11a) consistent with 6 electrons much like benzene, has a symmetrical bond distribution, and is highly aromatic. The planarity, shape, and electronic properties of boron clusters have been understood by applying the concept of aromaticity in both the ͞ domains (154).…”

Section: ϫmentioning

confidence: 99%

Clusters: A bridge across the disciplines of physics and chemistry

Jena

Castleman

2006

Proc. Natl. Acad. Sci. U.S.A.

228

161

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Section: ϫmentioning

confidence: 99%

Clusters: A bridge across the disciplines of physics and chemistry

Jena

Castleman

2006

Proc. Natl. Acad. Sci. U.S.A.

228

161

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“…However, simple total electronic counts lead sometimes to incorrect results [14,[53][54][55]. In addition, electron counting does not provide a quantitative value, so comparisons of aromaticity from different compounds are not possible.…”

Section: Introductionmentioning

confidence: 99%

A Critical Assessment of the Performance of Magnetic and Electronic Indices of Aromaticity

et al. 2010

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Abstract:The lack of reference aromatic systems in the realm of inorganic aromatic compounds makes the evaluation of aromaticity in all-metal and semimetal clusters a difficult task. To date, calculation of nucleus-independent chemical shifts (NICS) has been the most widely used method to discuss aromaticity in these systems. In the first part of this work, we briefly review our previous studies, showing some pitfalls of the NICS indicator of aromaticity in organic molecules. Then, we refer to our study on the performance of some aromaticity indices in a series of 15 aromaticity tests, which can be used to analyze the advantages and drawbacks of aromaticity descriptors. It is shown that indices based on the study of electron delocalization are the most accurate among those analyzed in the series of proposed tests, while NICS(1) zz and NICS(0) πzz present the best behavior among NICS indices. In the second part, we discuss the use of NICS and electronic multicenter indices (MCI) in inorganic clusters. In particular, we evaluate the aromaticity of two series of all-metal and semimetal clusters with predictable aromaticity trends by means of NICS and MCI. Results show that the expected trends are generally better reproduced by MCI than NICS. It is concluded that NICS(0) π and NICS(0) πzz are the kind of NICS that perform the best among the different NICS indices analyzed for the studied series of inorganic compounds.

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“…These remarkable properties lead boron to potentially important applications such as high-temperature semiconductors, 7 superconductor, 8 and high-energy density fuels. 9,10 Over the past few years, boron nanostructures have been extensively investigated both theoretically 1-3, [11][12][13][14][15][16][17][18][19][20][21] and experimentally. [14][15][16][17] The growing research interests are largely driven by the technological challenges of miniaturization of electronic devices.…”

Section: Introductionmentioning

confidence: 99%

Relative stability of planar versus double-ring tubular isomers of neutral and anionic boron cluster B20 and B20−

Bulusu

Gao

et al. 2006

The Journal of Chemical Physics

106

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High-level ab initio molecular-orbital methods have been employed to determine the relative stability among four neutral and anionic B 20 isomers, particularly the double-ring tubular isomer versus three low-lying planar isomers. Calculations with the fourth-order Møller-Plessset perturbation theory ͓MP4͑SDQ͔͒ and Dunning's correlation consistent polarized valence triple zeta basis set as well as with the coupled-cluster method including single, double, and noniteratively perturbative triple excitations and the 6-311G͑d͒ basis set show that the double-ring tubular isomer is appreciably lower in energy than the three planar isomers and is thus likely the global minimum of neutral B 20 cluster. In contrast, calculations with the MP4͑SDQ͒ level of theory and 6-311 +G͑d͒ basis set show that the double-ring anion isomer is appreciably higher in energy than two of the three planar isomers. In addition, the temperature effects on the relative stability of both 10 B 20 − and 11 B 20 − anion isomers are examined using the density-functional theory. It is found that the three planar anion isomers become increasingly more stable than the double-ring isomer with increasing the temperature. These results are consistent with the previous conclusion based on a joint experimental/simulated anion photoelectron spectroscopy study ͓B. Kiran et al., Proc. Natl. Acad. Sci. U.S.A. 102, 961 ͑2005͔͒, that is, the double-ring anion isomer is notably absent from the experimental spectra. The high stability of the double-ring neutral isomer of B 20 can be attributed in part to the strong aromaticity as charaterized by its large negative nucleus-independent chemical shift. The high-level ab initio calculations suggest that the planar-to-tubular structural transition starts at B 20 for neutral clusters but should occur beyond the size of B 20 − for the anion clusters.

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Aromaticity of Planar Boron Clusters Confirmed

Cited by 167 publications

References 76 publications

Clusters: A bridge across the disciplines of physics and chemistry

Clusters: A bridge across the disciplines of physics and chemistry

A Critical Assessment of the Performance of Magnetic and Electronic Indices of Aromaticity

Relative stability of planar versus double-ring tubular isomers of neutral and anionic boron cluster B20 and B20−

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