Cl@Si20X20 cages: evaluation of encapsulation nature, structural rigidity, and 29Si-NMR patterns using relativistic DFT calculations

MacLeod‐Carey, Desmond; Rodríguez‐Kessler, Peter L.; Muñoz-Castro, Álvaro

doi:10.1039/d3cp02371k

Cited by 3 publications

(1 citation statement)

References 86 publications

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“…We also observe a fourth contribution coming from the s orbital of the endohedral Cl − , which donates electron density to the

{\sigma ^{\ast} }

orbitals of the exohedrally located chlorine atoms, but this contribution is significantly smaller (Δ

{\rho 4}

, Δ E k =−5.1 kcal mol −1 ). These findings are in line with prior studies on [20]silafulleranes [118] …”

Section: Resultssupporting

confidence: 93%

Confined Lewis Pairs: Investigation of the X⁻→Si₂₀ Interaction in Halogen‐Encapsulating Silafulleranes

Gasevic,

Bamberg,

Wicke

et al. 2024

Angew Chem Int Ed

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A joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Si20Y20]− (X=F‐I Y=F‐I, H, Me, Et) and ‐[Cl@Si20H12Y8]− (Y=F‐I) is presented. First, we evaluated the structure‐determining template effect of Cl− in a systematic series of concave silapolyquinane model systems. Second, we investigated the X−→Si20 interaction energy ( ) as a function of X− and Y and found the largest values for electron‐withdrawing exohedral substituents Y. Given that X− ions can be considered as Lewis bases and empty Si20Y20 clusters as Lewis acids, we classify our inseparable host–guest complexes [X@Si20Y20]− as “confined Lewis pairs”. Third, 35Cl NMR spectroscopy proved to be highly diagnostic for an experimental assessment of the Cl−→Si20 interaction as the paramagnetic shielding and, in turn, (35Cl) of the endohedral Cl− ion correlate inversely with . Finally, we disclose the synthesis of [PPN][Cl@Si20Y20] (Y=Me, Et, Br) and provide a thorough characterization of these new silafulleranes.

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“…We also observe a fourth contribution coming from the s orbital of the endohedral Cl − , which donates electron density to the

{\sigma ^{\ast} }

orbitals of the exohedrally located chlorine atoms, but this contribution is significantly smaller (Δ

{\rho 4}

, Δ E k =−5.1 kcal mol −1 ). These findings are in line with prior studies on [20]silafulleranes [118] …”

Section: Resultssupporting

confidence: 93%

Confined Lewis Pairs: Investigation of the X⁻→Si₂₀ Interaction in Halogen‐Encapsulating Silafulleranes

Gasevic,

Bamberg,

Wicke

et al. 2024

Angew Chem Int Ed

View full text Add to dashboard Cite

show abstract

Confined Lewis Pairs: Investigation of the X⁻→Si₂₀ Interaction in Halogen‐Encapsulating Silafulleranes

Gasevic,

Bamberg,

Wicke

et al. 2024

Angewandte Chemie

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A joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Si20Y20]– (X– = F– ‐I– ; Y = F‐I, H, Me, Et) and Th‐[Cl@Si20H12Y8]– (Y = F‐I) is presented. First, we evaluated the structure‐determining template effect of Cl– in a systematic series of concave silapolyquinane model systems. Second, we investigated the X– →Si20 interaction energy (Eint) as a function of X– and Y and found the largest Eint values for electron‐withdrawing exohedral substituents Y. Given that X– ions can be considered as Lewis bases and empty Si20Y20 clusters as Lewis acids, we classify our inseparable host‐guest complexes [X@Si20Y20]– as “confined Lewis pairs”. Third, 35Cl NMR spectroscopy proved to be highly diagnostic for an experimental assessment of the Cl– →Si20 interaction as the paramagnetic shielding and, in turn, δ(35Cl) of the endohedral Cl– ion correlate inversely with Eint. Finally, we disclose the synthesis of [PPN][Cl@Si20Y20] (Y = Me, Et, Br) and provide a thorough characterization of these new silafulleranes.

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Structures and electronic properties of the TMn@W12O36 (TM = Cu, Ag and Au, n = 1–4) clusters

Wang,

Li,

et al. 2024

Struct Chem

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Cl@Si₂₀X₂₀ cages: evaluation of encapsulation nature, structural rigidity, and ²⁹Si-NMR patterns using relativistic DFT calculations

Abstract: The experimental characterization of Cl@Si20 endohedrals, featuring different ligands given by [Cl@Si20H20]- (1) [Cl@Si20H12Cl8]- (2), and [Cl@Si20Cl20]- (3), provides a variable encapsulation environment for the chloride anion. The favorable formation...

Cited by 3 publications

References 86 publications

Confined Lewis Pairs: Investigation of the X⁻→Si₂₀ Interaction in Halogen‐Encapsulating Silafulleranes

Confined Lewis Pairs: Investigation of the X⁻→Si₂₀ Interaction in Halogen‐Encapsulating Silafulleranes

Confined Lewis Pairs: Investigation of the X⁻→Si₂₀ Interaction in Halogen‐Encapsulating Silafulleranes

Structures and electronic properties of the TMn@W12O36 (TM = Cu, Ag and Au, n = 1–4) clusters

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Cl@Si20X20 cages: evaluation of encapsulation nature, structural rigidity, and 29Si-NMR patterns using relativistic DFT calculations

Abstract: The experimental characterization of Cl@Si20 endohedrals, featuring different ligands given by [Cl@Si20H20]- (1) [Cl@Si20H12Cl8]- (2), and [Cl@Si20Cl20]- (3), provides a variable encapsulation environment for the chloride anion. The favorable formation...

Cited by 3 publications

References 86 publications

Confined Lewis Pairs: Investigation of the X−→Si20 Interaction in Halogen‐Encapsulating Silafulleranes

Confined Lewis Pairs: Investigation of the X−→Si20 Interaction in Halogen‐Encapsulating Silafulleranes

Confined Lewis Pairs: Investigation of the X−→Si20 Interaction in Halogen‐Encapsulating Silafulleranes

Structures and electronic properties of the TMn@W12O36 (TM = Cu, Ag and Au, n = 1–4) clusters

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Product

Resources

About

Cl@Si₂₀X₂₀ cages: evaluation of encapsulation nature, structural rigidity, and ²⁹Si-NMR patterns using relativistic DFT calculations

Confined Lewis Pairs: Investigation of the X⁻→Si₂₀ Interaction in Halogen‐Encapsulating Silafulleranes

Confined Lewis Pairs: Investigation of the X⁻→Si₂₀ Interaction in Halogen‐Encapsulating Silafulleranes

Confined Lewis Pairs: Investigation of the X⁻→Si₂₀ Interaction in Halogen‐Encapsulating Silafulleranes