Selective <i>Endo</i> and <i>Exo</i> Binding of Alkali Metals to Corannulene

Spisak, Sarah N.; Zabula, Alexander V.; Filatov, Alexander S.; Rogachev, Andrey Yu.; Petrukhina, Marina A.

doi:10.1002/anie.201103028

Cited by 91 publications

(81 citation statements)

References 56 publications

(49 reference statements)

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“…Noncovalent functionalization of buckybowls (S and R) and contrasting their pattern with the planar coronene provides us important insights into the binding mechanism and the preferential binding surfaces and sites. The regio and stereo selectivity of metal ion binding to buckybowls is interesting in its own right, and this has been extensively studied . The structural, energetic and functional properties of buckybowls and their interaction with the models of π systems has also been reported …”

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confidence: 99%

Buckybowls as adsorbents for CO₂, CH₄, and C₂H₂: Binding and structural insights from computational study

2015

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Noncovalent functionalization of buckybowls sumanene (S), corannulene (R), and coronene (C) with greenhouse gases (GGs) such as CO2 , CH4 (M), and C2 H2 (A) has been studied using hybrid density functional theory. The propensity and preferences of these small molecules to interact with the concave and convex surfaces of the buckybowls has been quantitatively estimated. The results indicate that curvature plays a significant role in the adsorption of these small molecules on the π surface and it is observed that buckybowls have higher binding energies (BEs) compared with their planar counterpart coronene. The concave surface of the buckybowl is found to be more feasible for adsorption of small molecules. BEs of small molecules towards π systems is CO2 > A > M and the BEs of π systems toward small molecules is S > R > C. Obviously, the binding preference is dictated by the way in which various noncovalent interactions, such as π···π, lone pair···π, and CH···π manifest themselves on carbaneous surfaces. To delineate the intricate details of the interactions, we have employed Bader's quantum theory of atoms in molecule and localized molecular orbital energy decomposition analysis (LMO-EDA). LMO-EDA, which measures the contribution of various components and traces the physical origin of the interactions, indicates that the complexes are stabilized largely by dispersion interactions.

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Section: Introductionmentioning

confidence: 99%

Buckybowls as adsorbents for CO₂, CH₄, and C₂H₂: Binding and structural insights from computational study

2015

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“…[24,25] The other smallest bowl that can be mapped onto C 60 is sumanene C 21 H 12 , quite recently synthesized and which corresponds to a bowl with a six-carbon ring at the bottom. [24,[39][40][41]44,45,[47][48][49]51] However, in a previous work by our group, it has been shown that corannulene substituted with electron-withdrawing groups is able to form stable complexes with anions. [45,51] To the best of our knowledge, most studies in literature deal with the interaction of cations and these unsubstituted bowls.…”

Section: Introductionmentioning

confidence: 99%

Interaction between ions and substituted buckybowls: A comprehensive computational study

2014

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Complexes formed by substituted buckybowls derived from corannulene and sumanene with sodium cation or chloride anion have been computationally studied by using a variety of methods. Best results have been obtained with the SCS-MP2 method extrapolated to basis set limit, which reproduces the highest-level values obtained with the MP2.X method. All bowls form stable complexes with chloride anion, with stabilities ranging from -6 kcal/mol in the methylated corannulene derivative to -45 kcal/mol in the CN-substituted sumanene. The opposite trend is observed in sodium complexes, going from deeply attractive complexes with the methylated derivatives (-36 kcal/mol with sumanene derivative) to slightly repulsive ones in the CN-substituted bowls (2 kcal/mol in the corannulene derivative). Anion complexes are stabilized by large electrostatic interactions combined with smaller though significant dispersion and induction contributions. Conversely, cation complexes are stabilized by large induction contributions capable of holding together the bowl and the cation even in cases where the electrostatic interaction is repulsive. The effect of substitution is mainly reflected on changes in the molecular electrostatic potential of the bowl and, thus, in the electrostatic contribution to the interaction. Therefore, the variations in the stability of the complexes on substitution could be roughly predicted just considering the changes in the electrostatic interaction. However, other contributions also register changes mainly as a consequence of displacements on the position of the ion at the minimum, so the accurate prediction of the stability of this kind of complexes requires going further than the electrostatic approach.

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“…[17] Indeed, the controlled reduction of C 28 H 14 in diglyme using 1.2 equiv of cesium metal affords an intense green solution in 12 hours,which upon slow diffusion of hexanes at 10 8 8Cp roduces single crystals of 1 suitable for the X-ray diffraction studies (See the Supporting Information for more details). [17] Indeed, the controlled reduction of C 28 H 14 in diglyme using 1.2 equiv of cesium metal affords an intense green solution in 12 hours,which upon slow diffusion of hexanes at 10 8 8Cp roduces single crystals of 1 suitable for the X-ray diffraction studies (See the Supporting Information for more details).…”

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Site‐Directed Dimerization of Bowl‐Shaped Radical Anions to Form a σ‐Bonded Dibenzocorannulene Dimer

et al. 2018

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Designed site-directed dimerization of the monoanion radicals of a π-bowl in the solid state is reported. Dibenzo[a,g]corannulene (C H ) was selected based on the asymmetry of the charge/spin localization in the C H anion. Controlled one-electron reduction of C H with Cs metal in diglyme resulted in crystallization of a new dimer, [{Cs (diglyme)} (C H -C H ) ] (1), as revealed by single crystal X-ray diffraction study performed in a broad range of temperatures. The C-C bond length between two C H bowls (1.560(8) Å) measured at -143 °C does not significantly change upon heating of the crystal to +67 °C. The single σ-bond character of the C-C linker is confirmed by calculations. The trans-disposition of two bowls in 1 is observed with the torsion angles around the central C-C bond of 172.3(5)° and 173.5(5)°. A systematic theoretical evaluation of dimerization pathways of C H radicals confirmed that the trans-isomer found in 1 is energetically favored.

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Selective Endo and Exo Binding of Alkali Metals to Corannulene

Cited by 91 publications

References 56 publications

Buckybowls as adsorbents for CO₂, CH₄, and C₂H₂: Binding and structural insights from computational study

Buckybowls as adsorbents for CO₂, CH₄, and C₂H₂: Binding and structural insights from computational study

Interaction between ions and substituted buckybowls: A comprehensive computational study

Site‐Directed Dimerization of Bowl‐Shaped Radical Anions to Form a σ‐Bonded Dibenzocorannulene Dimer

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Selective Endo and Exo Binding of Alkali Metals to Corannulene

Cited by 91 publications

References 56 publications

Buckybowls as adsorbents for CO2, CH4, and C2H2: Binding and structural insights from computational study

Buckybowls as adsorbents for CO2, CH4, and C2H2: Binding and structural insights from computational study

Interaction between ions and substituted buckybowls: A comprehensive computational study

Site‐Directed Dimerization of Bowl‐Shaped Radical Anions to Form a σ‐Bonded Dibenzocorannulene Dimer

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Buckybowls as adsorbents for CO₂, CH₄, and C₂H₂: Binding and structural insights from computational study

Buckybowls as adsorbents for CO₂, CH₄, and C₂H₂: Binding and structural insights from computational study