Hemibuckminsterfullerene C30H12: X‐ray Crystal Structures of the Parent Hydrocarbon and of the Two‐Dimensional Organometallic Network {[Rh2(O2CCF3)4]3⋅(C30H12)}

Petrukhina, Marina A.; Andreini, Kristian W.; Peng, Li; Scott, Lawrence T.

doi:10.1002/anie.200460855

Cited by 116 publications

(87 citation statements)

References 34 publications

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“…3e) reveals that the six hub carbons are pyramidalized to an extent of 9.8° for C1 and 10.8° for C2 (Fig. 3e), both of which are bigger than sumanene (9.0°) 29 , and the latter is comparable to that of hemifullerene C 30 H 12 (10.8°) 31 .…”

Section: Synthesis Of Triazasumanenesmentioning

confidence: 93%

Enantioselective synthesis of a chiral nitrogen-doped buckybowl

et al. 2012

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Bowl-shaped aromatic compounds, namely buckybowls constitute a family of curved polycyclic aromatic carbons along with fullerenes and carbon nanotubes. Doping of heteroatoms to the carbon frameworks of such aromatic compounds drastically modulates their physical and chemical properties. In contrast to nitrogen-doped azafullerenes or carbon nanotubes, synthesis of azabuckybowls, nitrogen-doped buckybowls, remains an unsolved challenging task. Here we report the first enantioselective synthesis of a chiral azabuckybowl, triazasumanene. X-ray crystallographic analysis confirmed that the doping of nitrogen induces a more curved and deeper bowl structure than in all-carbon buckybowls. As a result of the deeper bowl structure, the activation energy for the bowl inversion (thermal flipping of the bowl structure) reaches an extraordinarily high value (42.2 kcal per mol). As the bowl inversion corresponds to the racemization process for chiral buckybowls, this high bowl inversion energy leads to very stable chirality of triazasumanene.

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Section: Synthesis Of Triazasumanenesmentioning

confidence: 93%

Enantioselective synthesis of a chiral nitrogen-doped buckybowl

et al. 2012

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“…These two dispositions resemble the arrangement found in the crystal packing for the homodimers of truxTTF and the related C 30 H 12 , implying a mixture of p-p and CH-p interactions. [30,32] All the optimized heterodimeric structures (1)(2)(3)(4) show close intermolecular contacts in the 2.5-3.7 range ( Figure S1 in the Supporting Information), indicative of stabilizing noncovalent interactions between both bowls.…”

Section: Resultsmentioning

confidence: 99%

“…Accurate calculations of the free energy of complexation suggested that only the staggered conformer in which one dithiole ring is placed inside the bowl These are not the final page numbers! ÞÞ Full Paper 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 8 9 9 10 10 11 11 12 12 13 13 14 14 15 15 16 16 17 17 18 18 19 19 20 20 21 21 22 22 23 23 24 24 25 25 26 26 27 27 28 28 29 29 30 30 31 31 32 32 33 33 34 34 35 35 36 36 37 37 38 38 39 39 40 40 41 41 42 42 43 43 44 44 45 45 46 46 47 47 48 48 49 49 50 50 51 51 52 52 53 53 54 54 55 55 56 56 57 57 basin could be formed in solution for truxTTF·C 32 32 H 12 , the assignment of the charge-separated state was extremely difficult, but on the basis of earlier findings, its existence is regarded ...…”

Section: Discussionmentioning

confidence: 99%

Complexation and Electronic Communication between Corannulene‐Based Buckybowls and a Curved Truxene‐TTF Donor

Gallego

Calbo

Calderón

et al. 2017

Chemistry A European J

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The association behavior of an electron-donating, bowl-shaped, truxene-based tetrathiafulvalene (truxTTF) with two corannulene-based fullerene fragments, ÀC 32 H 12 and C 38 H 14 À, is investigated in several solvents. Formation of 1:1 complexes is followed by absorption titrations and complemented by density functional theory (DFT) calculations. The binding constants are in the range log K a = 2.9-3.5. DFT calculations reveal that the most stable arrangement is the conformation in which the 1,3-dithiole ring of truxTTF is placed inside the concave cavity of the corannulene derivative. This arrangement is confirmed experimentally by NMR measurements, and implies that a combination of p-p and CH-p interactions is the driving force for association. Timedependent DFT calculations reproduce the experimental UV/ Vis titrations and provide a detailed understanding of the spectral changes observed. Femtosecond transient absorption studies reveal the processes occurring after photoexcitation of either C 32 H 12 or C 38 H 14 and their supramolecular associates with truxTTF. In the case of truxTTF·C 38 H 14 , photoexcitation yields the charge-separated state truxTTFC + ·C 38 H 14 C À with a lifetime of approximately 160 ps.

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“…At this point, we want to point out that the degree of pyramidalization should be used with caution to rationalize the reactivity of these PAHs. For instance, the experimental (X-ray crystallography) derived average POAV angles follow the trend: 8.3º (1), [38] 9.6 (2), [7] 9.0º (3), [39] 10.7º (4), [40] 12.1º (5) [41] and 11.6 º (C 60 ), [3] which indicates that cyclopentacorannulene 2 and circumtrindene 5…”

Section: A] Reactant Complex (Rc) Energy: ∆E Rc = E Rc -E(buckybowl) mentioning

confidence: 99%

Reactivity and Selectivity of Bowl‐Shaped Polycyclic Aromatic Hydrocarbons: Relationship to C₆₀

García-Rodeja

Solà

Bickelhaupt

et al. 2015

Chemistry A European J

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The Diels-Alder reactivity of different bowl-shaped polycyclic aromatic hydrocarbons (namely, corannulene, cyclopentacorannulene, diindenochrysene, hemifullerene, and circumtrindene) has been explored computationally within the Density Functional Theory framework. To this end, both the increase of the reactivity with the size of the buckybowl and the complete [6,6]-regioselectivity in the process have been analyzed in detail using the activation strain model of reactivity in combination with the energy decomposition analysis method. Our results have been compared to the parent C 60 fullerene, which also produces the corresponding [6,6]-cycloadduct exclusively. It is found that the behavior of the considered buckybowls resembles, in general, that of C 60 . Whereas the interaction energy between the deformed reactants along the reaction coordinate mainly controls the regioselectivity of the process, it is the interplay between the activation strain energy and the transition state interaction which governs the reactivity of the system.

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Hemibuckminsterfullerene C₃₀H₁₂: X‐ray Crystal Structures of the Parent Hydrocarbon and of the Two‐Dimensional Organometallic Network {[Rh₂(O₂CCF₃)₄]₃⋅(C₃₀H₁₂)}

Cited by 116 publications

References 34 publications

Enantioselective synthesis of a chiral nitrogen-doped buckybowl

Enantioselective synthesis of a chiral nitrogen-doped buckybowl

Complexation and Electronic Communication between Corannulene‐Based Buckybowls and a Curved Truxene‐TTF Donor

Reactivity and Selectivity of Bowl‐Shaped Polycyclic Aromatic Hydrocarbons: Relationship to C₆₀

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Hemibuckminsterfullerene C30H12: X‐ray Crystal Structures of the Parent Hydrocarbon and of the Two‐Dimensional Organometallic Network {[Rh2(O2CCF3)4]3⋅(C30H12)}

Cited by 116 publications

References 34 publications

Enantioselective synthesis of a chiral nitrogen-doped buckybowl

Enantioselective synthesis of a chiral nitrogen-doped buckybowl

Complexation and Electronic Communication between Corannulene‐Based Buckybowls and a Curved Truxene‐TTF Donor

Reactivity and Selectivity of Bowl‐Shaped Polycyclic Aromatic Hydrocarbons: Relationship to C60

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Hemibuckminsterfullerene C₃₀H₁₂: X‐ray Crystal Structures of the Parent Hydrocarbon and of the Two‐Dimensional Organometallic Network {[Rh₂(O₂CCF₃)₄]₃⋅(C₃₀H₁₂)}

Reactivity and Selectivity of Bowl‐Shaped Polycyclic Aromatic Hydrocarbons: Relationship to C₆₀