Rationalizing the relative abundances of trimetallic nitride template-based endohedral metallofullerenes from aromaticity measures

Garcia‐Borràs, Marc; Osuna, Sílvia; Luis, Josep M.; Solà, Miquel

doi:10.1039/c7cc01750b

Cited by 5 publications

(7 citation statements)

References 22 publications

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“…Following the line started with our previous study, we generalized the ALA index to expand its scope [32]. In this work, we proposed the normalization of the ALA index per number of rings present in the fullerene structure to allow the comparison between fullerenes with different number of carbon atoms, as follows:…”

Section: Understanding the Relative Abundances Of Tnt-based Endohedramentioning

confidence: 99%

“…As we will show in this review, aromaticity plays also a key role in determining the most stable isomer for the EMF encapsulation [31]. Aromaticity can also be used to rationalize the experimental EMF abundances obtained in the laboratory [32].…”

Section: Introductionmentioning

confidence: 98%

“…The formal charge transfer that takes place on EMFs [25] has severe consequences on the reactivity [31,33,34], aromaticity [32,35,36], and relative stabilities [28] of these compounds. Empty fullerenes generally react with those bonds situated between hexagons (i.e called [6,6]), whereas EMFs and negatively charged C60 often prefer [5,6] bonds [31,37].…”

Section: Introductionmentioning

confidence: 99%

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The key role of aromaticity in the structure and reactivity of C60 and endohedral metallofullerenes

Garcia‐Borràs

Luis

Solà

et al. 2017

Inorganica Chimica Acta

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In this review, we show that the local aromaticity of C60 and endohedral metallofullerenes (EMFs) is a key factor to understand and predict their structure and reactivity. We report recent examples provided by our group that highlight the importance of aromaticity in C60 and EMFs. First example discusses the regioselectivity of Diels-Alder reactions in reduced C60; the second one analyzes how aromaticity stabilizes the most suitable hosting cages in EMFs; the third one determines the effect of aromaticity in the relative abundances of EMFs; the fourth one shows a relationship between aromaticity and the stability of EMF adducts formed in Bingel-Hirsch (BH) reactions; and the last one proposes structural criteria to predict the regioselectivity in BH reactions based on the local aromaticity of EMFs.

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Section: Understanding the Relative Abundances Of Tnt-based Endohedramentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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The key role of aromaticity in the structure and reactivity of C60 and endohedral metallofullerenes

Garcia‐Borràs

Luis

Solà

et al. 2017

Inorganica Chimica Acta

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“…It is indicated that the structures of fullerene isomers also play a significant role in the electron-transfer character of inner moieties. Moreover, Garcia-Borras and co-workers have pointed out that cage aromaticity is the most important stabilizing factor in the process of EMF formation. , In fact, except for U@C 74 and U@C 82 series, mono-EMFs U@C 70 and U@C 72 were detected in experiments dating back to 1992 by Smalley and co-workers . The structures of U@C 70 and U@C 72 were only characterized by FT-ICR mass spectral analysis but without any detailed structural characterization.…”

Section: Introductionmentioning

confidence: 99%

Encapsulation of Monometal Uranium into Fullerenes C_2n(2n= 70–74): Important Ionic U⁴⁺C_2n^4–Characters and Covalent U-Cage Bonding Interactions

Zhao

et al. 2019

Inorg. Chem.

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By using density functional theory calculations combined with statistical thermodynamic analyses, the stabilization performance of a series of fullerene cages C2n (2n = 70–74) via encapsulating monometal uranium was systematically and thoroughly investigated. Results indicate that fullerene cages D 5h (8149)-C70 and D 3h (14246)-C74 obeying the isolated pentagon rule and C 2(10612)-C72 featured with one pentalene moiety were the most promising candidates to encage uranium. Subsequent Mulliken spin density distribution and frontier molecular orbital analyses suggest that four formal electron transfer occurs from monometal U to above the carbon cages. There also exists a high degree of covalent character between the atom U and fullerenes C2n based on Mayer bond order and quantum theory of atoms in molecule (QTAIM) analyses, indicative of the cooperative stabilization by both ionic and covalent bonding interactions. In addition, investigations on the above-mentioned U@C2n isomers and other favorable candidates (U@C s (8094)-C70, U@C 1(10610)-C72, U@C 1(13393)-C74, and U@C 1(14049)-C74) reveal that these isomers could be closely linked via simple C2 addition and Stone–Wales transformation. These results will provide a systematic understanding on U-based endohedral metallofullerenes (EMFs) and also might be helpful for further exploration of EMF growth mechanisms.

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“…Garcia‐Borràs et al have suggested that the maximum aromaticity criteria correlates with the most suitable host carbon cage for a given metallic cluster in endohedral fullerenes . The same group, computed aromaticity using a number of different codes and showed that the normalized additive local aromaticity index can be used to explain the relative abundance of the trimetallic endohedral fullerenes …”

Section: Introductionmentioning

confidence: 99%

Electronic structure calculation of vanadium‐and scandium‐based endohedral fullerenes VSc₂N@C_2n (2n = 70, 76, 78, 80)

Bhusal

Baruah

Yamamoto

et al. 2018

Int J of Quantum Chemistry

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We present candidate structures for the most stable isomers for the VSc 2 N@C 70 , VSc 2 N@C 76 , VSc 2 N@C 78 , and VSc 2 N@C 80 using 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 VSc 2 N@C 80 isomer as the most stable structure. The structural analysis shows that only VSc 2 N@C 70 has a non-IPR cage among the four endohedral fullerenes. Respectively, VSc 2 N@C 70 and VSc 2 N@C 76 have nearly degenerate spin states with total spin S = 0 and S = 1.All the lowest energy cages are energetically stable and show significant electron accepting capacity comparable to C 60 .degenerate spin states, quasiparticle gap, magnetic spin moment 1 | INTRODUCTION Carbon cages in endohedral fullerenes serve as a robust container to accommodate some units like atoms, molecules, and clusters. Just after the discovery of Buckminsterfullerene C 60 in 1985 by Smalley and coworkers, [1] the endohedral fullerene La@C 60 was synthesized for the first time in the same year. [2] The attention on endohedral fullerenes grew after its macroscopic production by Huffman and his group in 1990. [3] Still, the production of endohedral fullerenes was low and was about only 1% of the total production of empty fullerene cages. Harry Dorn and coworkers in 1999 successfully synthesized tri-scandium nitride cluster fullerene Sc 3 N@C 80 using N 2 gas environment in the Krätschmer-Huffman arc generator, which greatly enhances the yield of endohedral fullerenes. [4] The higher kinetic stability obtained from the gap opening between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) makes this nitride cluster fullerene (NCF) the most abundant fullerene after C 60 and C 70 . Subsequently, other synthesis methods for endohedral fullerenes were reported, which produced endohedral fullerenes in macroscopic amounts. [5][6][7][8][9] Attractive properties like large surface areas, high electron accepting capacity, and empty space to accommodate atoms, molecules, and cluster for potential use in different applications such as medicine and electronics make the fullerenes and endohedral fullerenes one of the active areas of research. [10][11][12][13][14][15][16][17][18][19][20] The stability of fullerenes is driven by the isolated pentagon rule (IPR). This rule is strictly followed by empty cage fullerenes, and it grants stability to only those fullerenes in which all the pentagonal sides are shared by hexagons. It has been pointed out that it is not possible for the C 20 -C 58 , C 62 -C 68 cages to satisfy the isolated pentagon rule. These carbon cages have high strain, and as a result, are unstable and difficult to isolate.In the endohedral form, however, the complexation releases large strain energy, which leads to f...

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Rationalizing the relative abundances of trimetallic nitride template-based endohedral metallofullerenes from aromaticity measures

Abstract: The synthesis of endohedral metallofullerenes (EMFs) from a carbon soot sample leads to a variety of EMFs that are obtained in different relative abundances. In this work, we show that these abundances can be predicted from aromaticity calculations.

Cited by 5 publications

References 22 publications

The key role of aromaticity in the structure and reactivity of C60 and endohedral metallofullerenes

The key role of aromaticity in the structure and reactivity of C60 and endohedral metallofullerenes

Encapsulation of Monometal Uranium into Fullerenes C_2n(2n= 70–74): Important Ionic U⁴⁺C_2n^4–Characters and Covalent U-Cage Bonding Interactions

Electronic structure calculation of vanadium‐and scandium‐based endohedral fullerenes VSc₂N@C_2n (2n = 70, 76, 78, 80)

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Rationalizing the relative abundances of trimetallic nitride template-based endohedral metallofullerenes from aromaticity measures

Abstract: The synthesis of endohedral metallofullerenes (EMFs) from a carbon soot sample leads to a variety of EMFs that are obtained in different relative abundances. In this work, we show that these abundances can be predicted from aromaticity calculations.

Cited by 5 publications

References 22 publications

The key role of aromaticity in the structure and reactivity of C60 and endohedral metallofullerenes

The key role of aromaticity in the structure and reactivity of C60 and endohedral metallofullerenes

Encapsulation of Monometal Uranium into Fullerenes C2n(2n= 70–74): Important Ionic U4+C2n4–Characters and Covalent U-Cage Bonding Interactions

Electronic structure calculation of vanadium‐and scandium‐based endohedral fullerenes VSc2N@C2n (2n = 70, 76, 78, 80)

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Encapsulation of Monometal Uranium into Fullerenes C_2n(2n= 70–74): Important Ionic U⁴⁺C_2n^4–Characters and Covalent U-Cage Bonding Interactions

Electronic structure calculation of vanadium‐and scandium‐based endohedral fullerenes VSc₂N@C_2n (2n = 70, 76, 78, 80)