+ Site Statistics
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

Violating the isolated pentagon rule (IPR): endohedral non-IPR C98 cages of Gd2@C98



Violating the isolated pentagon rule (IPR): endohedral non-IPR C98 cages of Gd2@C98



Inorganic Chemistry 51(4): 2039-2045



The geometric, electronic structure, and thermodynamic stability of large gadolinium-containing endohedral metallofullerenes, Gd(2)@C(98), have been systematically investigated by comprehensive density functional theory calculations combined with statistical mechanics treatments. The Gd(2)@C(2)(230924)-C(98) structure, which satisfies the isolated-pentagon rule (IPR), is determined to possess the lowest energy followed with some stable non-IPR isomers. In order to clarify the relative stabilities at elevated temperatures, entropy contributions are taken into account on the basis of the Gibbs energy at the B3LYP level for the first time. Interestingly, a novel non-IPR Gd(2)@C(1)(168785)-C(98) isomer which has one pair of pentagon adjacency is more thermodynamically stable than the lowest energy IPR species within a wide temperature interval related to fullerene formation. Therefore, the Gd(2)@C(1)(168785)-C(98) is predicted to be the most proper isomer obtained experimentally, which is the largest non-IPR carbon cage found so far. Our findings demonstrate that interaction between metals and carbon cages could stabilize the fused pentagons effectively, and thus, the non-IPR isomers should not be ignored in some cases of endohedral metallofullerenes. The IR features of Gd(2)@C(98) are simulated to assist its future experimental characterization.

Please choose payment method:






(PDF emailed within 0-6 h: $19.90)

Accession: 056872724

Download citation: RISBibTeXText

PMID: 22288613

DOI: 10.1021/ic201585j


Related references

Isolated pentagon rule violating endohedral metallofullerenes explained using the Hückel rule: a statistical mechanical study of the C84 Isomeric Set. Journal of Computational Chemistry 36(3): 146-150, 2015

Violating the isolated pentagon rule (IPR): the endohedral non-IPR C70 cage of Sc3N@C70. Angewandte Chemie 46(8): 1256-1259, 2007

Diels-Alder reaction on free C₆₈ fullerene and endohedral Sc₃N@C₆₈ fullerene violating the isolated pentagon rule: importance of pentagon adjacency. Chemistry An Asian Journal 9(9): 2604-2611, 2014

C₇₄ endohedral metallofullerenes violating the isolated pentagon rule: a density functional theory study. Nanoscale 4(15): 4530-4536, 2012

Is the isolated pentagon rule merely a suggestion for endohedral fullerenes? The structure of a second egg-shaped endohedral fullerene--Gd3N@C(s)(39663)-C82. Journal of the American Chemical Society 130(25): 7854-7855, 2008

Is the isolated pentagon rule always satisfied for metallic carbide endohedral fullerenes?. Inorganic Chemistry 51(21): 11223-5, 2012

The Regioselectivity of Bingel-Hirsch Cycloadditions on Isolated Pentagon Rule Endohedral Metallofullerenes. Angewandte Chemie 55(7): 2374-2377, 2016

Tb3N@C84: an improbable, egg-shaped endohedral fullerene that violates the isolated pentagon rule. Journal of the American Chemical Society 128(35): 11352-3, 2006

Sc3N@C68: folded pentalene coordination in an endohedral fullerene that does not obey the isolated pentagon rule. Angewandte Chemie 42(8): 900-903, 2003

Sc2S@C(s)(10528)-C72: a dimetallic sulfide endohedral fullerene with a non isolated pentagon rule cage. Journal of the American Chemical Society 134(18): 7851-7860, 2012

Nonclassical fullerenes with a heptagon violating the pentagon adjacency penalty rule. Journal of Computational Chemistry 31(8): 1715-1721, 2010

A geometric constraint, the head-to-tail exclusion rule, may be the basis for the isolated-pentagon rule in fullerenes with more than 60 vertices. Proceedings of the National Academy of Sciences of the United States of America 105(49): 19142-7, 2008

New Isolated-Pentagon-Rule Isomer of C92 Isolated as Trifluoromethyl and Chlorido Derivatives: C92(38)(CF3)14/16 and C92(38)Cl20/22. Inorganic Chemistry 54(22): 10527-9, 2015

Nitrogen violation of the isolated pentagon rule. Nano Letters 6(5): 890-895, 2006

Electronic structure and stability of fullerene C82 isolated-pentagon-rule isomers. Journal of Physical Chemistry. a 115(44): 12315-12320, 2011