On the search of stable, aromatic and ionic endohedral compounds of C28: A theoretical study

Miralrio, Alan; Sansores, Luis Enrique

doi:10.1016/j.comptc.2016.03.010

Cited by 31 publications

(76 citation statements)

References 38 publications

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“…Interestingly, the electronic structure resembling an 1S 2 1P 6 1D 10 1F 14 electronic configuration accommodating the 32 valence electrons, as discussed above, accounts for a favorable spherical aromatic behavior as expected from the Hirsch 2( N + 1) 2 rule . Hence, M@C 28 (M = Zr, Hf, Th) and [U@C 28 ] 2+ , in addition to

C_{28}^{4 -}

, can be ascribed as spherical aromatic systems where the electronic shells resulting from the π‐system and the endohedral atom exhibits a close‐shell structure . Furthermore, both open‐shell counterparts, namely,

C_{28}^{6 -}

U@C 28 , having 34‐ve, can also be related to spherical aromatic compounds owing to the extension of the Hirsch rule to open‐shell spherical compounds, which has been proved by Poater and Solà .…”

Section: Resultsmentioning

confidence: 74%

“…[54][55][56][57] Hence, M@C 28 (M 5 Zr, Hf, Th) and [U@C 28 ] 21 , in addition to C 42 28 , can be ascribed as spherical aromatic systems where the electronic shells resulting from the psystem and the endohedral atom exhibits a close-shell structure. [32] Furthermore, both open-shell counterparts, namely, C 62 28 U@C 28 , having 34-ve, can also be related to spherical aromatic compounds owing to the extension of the Hirsch rule to open-shell spherical compounds, which has been proved by Poater and Sol a. [58] Hence, the studied endohedral fullerenes exhibit an spherical aromatic behavior as given by electron count considerations.…”

Section: Full Papermentioning

confidence: 79%

“…Moreover, other prominent M@C 28 species were obtained using different tetravalent atoms such as the group 4 metals titanium, zirconium, and hafnium, as observed from their high relative abundances in the mass spectra . In addition, the incorporation of several tetravalent atoms in M@C 28 has been studied theoretically …”

Section: Introductionmentioning

confidence: 99%

“…[28] In addition, the incorporation of several tetravalent atoms in M@C 28 has been studied theoretically. [32] The 32-ve principle requires the presence of filled s-, p-, d-, and f-like shells, in the complete electronic structure. Thus the bonding between the C 28 fullerene and endohedral f-block metals, such as the actinides, can exhibit dominant f-type character.…”

Section: Introductionmentioning

confidence: 99%

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Evaluation of bonding, electron affinity, and optical properties of M@C₂₈ (M = Zr, Hf, Th, and U): Role of d‐ and f‐orbitals in endohedral fullerenes from relativistic DFT calculations

Muñoz-Castro

King²

2016

J Comput Chem

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The experimentally characterized endohedral metallic fullerenes involving the small C cage, has shown to be able to encapsulate zirconium, hafnium, and uranium atoms, among other elements. Here, we explore the formation and nature of concentric bonds from purely d- to f-block elements, given by Zr, Hf, and uranium, along a borderline metal between such blocks, thorium. We explore the interplay of d- and f-orbitals in the chemistry of the early actinides, where the features of a d- or f-block metal can be mixed. Our results indicate that the bonding of Th@C involves contributions from both d- and f-type bonds, as characteristic of this early actinide element. Even uranium in U@C , also exhibits a contribution from d-type bonds in addition to its relevant f-block character. Electron affinity and optical properties were evaluated to gain more insights into the variation of these molecular properties in this small endohedral fullerene, along Zr, Hf, Th, and U. The current results, allows to unravel the role of (n - 1)d and (n - 2)f orbitals in confined elements ranging from d- to f-blocks, which can be useful to gain a deeper understanding of the bonding situation in other endohedral species. © 2016 Wiley Periodicals, Inc.

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C_{28}^{4 -}

C_{28}^{6 -}

Section: Resultsmentioning

confidence: 74%

Section: Full Papermentioning

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Evaluation of bonding, electron affinity, and optical properties of M@C₂₈ (M = Zr, Hf, Th, and U): Role of d‐ and f‐orbitals in endohedral fullerenes from relativistic DFT calculations

Muñoz-Castro

King²

2016

J Comput Chem

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“…Soon after the discovery of C 60 fullerene by Kroto et al., the idea of encapsulating atoms, ions or molecules became popular since the hollow carbon‐closed cages could serve as versatile containers for other systems . The presence of metal transition compounds inside different types of fullerenes enhances the stability and donor‐acceptor properties .…”

Section: Introductionmentioning

confidence: 99%

Are Small Quasi‐Fullerenes Capable of Encapsulating Trimetallic Nitrides A_3‐xB_xN (A, B =Sc, Y, La,x=0‐3)? A DFT Study

et al. 2018

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The capacity of small quasi‐fullerenes (C48‐q and C60‐q, q stands for quasi) to encapsulate trimetallic nitride clusters; A3‐xBxN (A, B=Sc, Y, La, x=0‐3) was investigated by applying Density Functional Theory (DFT). Optimized geometries and the computation of ΔG formation energies, ΔΕHOMO‐LUMO energy values, chemical potential, chemical hardness and aromaticity were all performed in order to understand chemical reactivity and thermal stability of these novel quasi‐metallofullerenes. Moreover, the donor‐acceptor properties of the quasi‐metallofullerenes systems compared to the bare quasi‐fullerene cages are also analyzed. Finally, to understand the effect of temperature at which quasi‐fullerenes could be subjected to, ab initio molecular dynamics (MD) was also performed. The main conclusion of this report is that small quasi‐fullerenes are capable of encapsulating trimetallic nitride clusters, and that the donor‐acceptor properties are enhanced due to the presence of clusters.

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Exohedral Diels‐Alder Reactivity of Endohedral Metallofullerene C₃₆

Santha Bhaskaran,

Romero del Blanco,

Romero‐Rivera

et al. 2024

Chemistry A European J

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Understanding the exohedral reactivity of metallofullerenes is crucial for its application in various fields. By systematically controlling the trapped species inside the fullerene its reactivity can be tamed. In this work we report the preferential position of 3d metal atoms inside the C36 cage and their effect on exohedral reactivity in comparison with the neutral and the dianionic cage. The Diels‐Alder (DA) reaction between butadiene and all non‐equivalent [5‐5], [6‐5] and [6‐6] C‐C bonds on the fullerene cage was considered for the analysis, by using density functional theory at the S12g/TZ2P level including COSMO solvation model to elucidate the complete mechanistic pathways. Our results indicate that the preferential position of the metal ion is at the position close to the upper hexagon, and that the general trend in the reactivity of bonds follows the order [5‐5] > [6‐5] > [6‐6]. Moreover, the encapsulation of metal atoms further enhances the reactivity of these bonds, by distorting the system and delocalizing the LUMOs all over the cage.

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On the search of stable, aromatic and ionic endohedral compounds of C28: A theoretical study

Cited by 31 publications

References 38 publications

Evaluation of bonding, electron affinity, and optical properties of M@C₂₈ (M = Zr, Hf, Th, and U): Role of d‐ and f‐orbitals in endohedral fullerenes from relativistic DFT calculations

Evaluation of bonding, electron affinity, and optical properties of M@C₂₈ (M = Zr, Hf, Th, and U): Role of d‐ and f‐orbitals in endohedral fullerenes from relativistic DFT calculations

Are Small Quasi‐Fullerenes Capable of Encapsulating Trimetallic Nitrides A_3‐xB_xN (A, B =Sc, Y, La,x=0‐3)? A DFT Study

Exohedral Diels‐Alder Reactivity of Endohedral Metallofullerene C₃₆

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On the search of stable, aromatic and ionic endohedral compounds of C28: A theoretical study

Cited by 31 publications

References 38 publications

Evaluation of bonding, electron affinity, and optical properties of M@C28 (M = Zr, Hf, Th, and U): Role of d‐ and f‐orbitals in endohedral fullerenes from relativistic DFT calculations

Evaluation of bonding, electron affinity, and optical properties of M@C28 (M = Zr, Hf, Th, and U): Role of d‐ and f‐orbitals in endohedral fullerenes from relativistic DFT calculations

Are Small Quasi‐Fullerenes Capable of Encapsulating Trimetallic Nitrides A3‐xBxN (A, B =Sc, Y, La,x=0‐3)? A DFT Study

Exohedral Diels‐Alder Reactivity of Endohedral Metallofullerene C36

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Evaluation of bonding, electron affinity, and optical properties of M@C₂₈ (M = Zr, Hf, Th, and U): Role of d‐ and f‐orbitals in endohedral fullerenes from relativistic DFT calculations

Evaluation of bonding, electron affinity, and optical properties of M@C₂₈ (M = Zr, Hf, Th, and U): Role of d‐ and f‐orbitals in endohedral fullerenes from relativistic DFT calculations

Are Small Quasi‐Fullerenes Capable of Encapsulating Trimetallic Nitrides A_3‐xB_xN (A, B =Sc, Y, La,x=0‐3)? A DFT Study

Exohedral Diels‐Alder Reactivity of Endohedral Metallofullerene C₃₆