DFT study of the interaction free energy of π–π complexes of fullerenes with buckybowls and viologen dimers

Casella, Girolamo; Saielli, Giacomo

doi:10.1039/c1nj20117d

Cited by 34 publications

(29 citation statements)

References 49 publications

(22 reference statements)

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“…In the presence of methyl viologen 21 (MV 2+ ), [17] the catalytic activity of triad 1 but not control 6 further increased by A/D (1+21) /A /D (1) = 1.23 (Figure 3c). CD titrations indicated that the p-acidic MV 2+ intercalates between the two fullerenes in triad 1 (EC 50 = 0.63 AE 0.05 mm,F igure 2c,F igure S6), thus attracting electron density from the active site (increasing intrinsic p acidity) and expanding the extent of electronic communication, including polarizability (increasing induced p acidity).…”

Section: Angewandte Chemiementioning

confidence: 99%

Remote Control of Anion–π Catalysis on Fullerene‐Centered Catalytic Triads

et al. 2018

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The design, synthesis and evaluation of catalytic triads composed of a central C60 fullerene with an amine base on one side and polarizability enhancers on the other side are reported. According to an enolate addition benchmark reaction, fullerene–fullerene–amine triads display the highest selectivity in anion–π catalysis observed so far, whereas NDI–fullerene–amine triads are not much better than fullerene–amine controls (NDI=naphthalenediimide). These large differences in activity are in conflict with the small differences in intrinsic π acidity, that is, LUMO energy levels and π holes on the central fullerene. However, they are in agreement with the high polarizability of fullerene–fullerene–amine triads. Activation and deactivation of the fullerene‐centered triads by intercalators and computational data on anion binding further indicate that for functional relevance, intrinsic π acidity is less important than induced π acidity, that is, the size of the oriented macrodipole of polarizable π systems that emerges only in response to the interaction with anions and anionic transition states. The resulting transformation is thus self‐induced, the anionic intermediates and transition states create their own anion–π catalyst.

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Section: Angewandte Chemiementioning

confidence: 99%

Remote Control of Anion–π Catalysis on Fullerene‐Centered Catalytic Triads

et al. 2018

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“…Due to the complexity and size of organic molecular crystals, most theoretical studies up to date have only addressed the energetics of the interaction between isolated molecular bowls with various metal cations [23][24][25][26][27][28] or the energetics of small assemblies such as corannulene dimers [29][30][31][32] or p-bowl-fullerene binary systems [33][34][35]. Only recently, several studies have explored the optical and vibrational properties of corannulene-based crystals [14,16,36,37].…”

Section: Introductionmentioning

confidence: 99%

Electronic transport properties of selected carbon π-bowls with different size, curvature and solid state packing

Wang

Petrukhina

Margine

2015

Carbon

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“…In particular, buckycatcher I has become a popular benchmark to develop new density functionals . Theoretical calculations have made important contributions to the design of new fullerene receptors, and to shed light into the properties of multishell fullerenes, where a fullerene hosts a smaller cage . In particular our research group has been interested in the study of new fullerene receptors .…”

Section: Introductionmentioning

confidence: 99%

On the estimation of the strength of supramolecular complexes of fullerenes

Denis

2018

Int J of Quantum Chemistry

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The accurate estimation of the free energy changes in solution for supramolecular complexes is one of the most important challenges for quantum chemistry in this century. In general, there is a good correlation between the association constants determined experimentally and the gas phase binding energies calculated using the most popular density functional methods. However, when the receptors adopt very different structures in the gas and condensed phase, this approach does not work, leading to unreliable predictions. We discuss this problem in detail using three popular fullerene receptors: Aida's dimeric porphyrins, buckycatchers I, and II. We found that it is possible to obtain a reliable order of affinities using gas phase binding energies when a special attention is put on analyzing the structure adopted by the receptor in the gas and condensed phases.

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DFT study of the interaction free energy of π–π complexes of fullerenes with buckybowls and viologen dimers

Cited by 34 publications

References 49 publications

Remote Control of Anion–π Catalysis on Fullerene‐Centered Catalytic Triads

Remote Control of Anion–π Catalysis on Fullerene‐Centered Catalytic Triads

Electronic transport properties of selected carbon π-bowls with different size, curvature and solid state packing

On the estimation of the strength of supramolecular complexes of fullerenes

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