X-ray Quality Geometries of Geodesic Polyarenes from Theoretical Calculations:  What Levels of Theory Are Reliable?

Petrukhina, Marina A.; Andreini, Kristian W.; Mack, James; Scott, Lawrence T.

doi:10.1021/jo050233e

Cited by 197 publications

(204 citation statements)

References 15 publications

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“…6A) are 1.42 (ab), 1.38 (bc), 1.45 (cd), and 1.40 (de) Å, respectively, which are identical to the distances reported in the x-ray crystal structures of corannulene (27) except that the rim (de) in 3b is slightly longer than in corannulene (1.38 Å), probably because of the angle constraint from the fused lactam ring. Among all four types of corannulene carbon-carbon bonds, the flank (cd) has the least double bond character.…”

Section: Resultssupporting

confidence: 80%

“…Our main concern was the competition between two self-assembly processes, either edgeto-edge binding through intermolecular hydrogen bonding or van der Waals stacking. Recently, density functional theory at B3LYP/6-31G* was shown to best reproduce the x-ray-derived corannulene geometry (27). We therefore chose to use B3LYP/6-31G* in Gaussian 03 (28) to optimize geometries in all series 3 monomer and dimer structures.…”

Section: Resultsmentioning

confidence: 99%

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Chemical mimicry of viral capsid self-assembly

Olson

Keinan

2007

Proc. Natl. Acad. Sci. U.S.A.

102

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Stable structures of icosahedral symmetry can serve numerous functional roles, including chemical microencapsulation and delivery of drugs and biomolecules, epitope presentation to allow for an efficient immunization process, synthesis of nanoparticles of uniform size, observation of encapsulated reactive intermediates, formation of structural elements for supramolecular constructs, and molecular computing. By examining physical models of spherical virus assembly we have arrived at a general synthetic strategy for producing chemical capsids at size scales between fullerenes and spherical viruses. Such capsids can be formed by self-assembly from a class of molecules developed from a symmetric pentagonal core. By designing chemical complementarity into the five interface edges of the molecule, we can produce self-assembling stable structures of icosahedral symmetry. We considered three different binding mechanisms: hydrogen bonding, metal binding, and formation of disulfide bonds. These structures can be designed to assemble and disassemble under controlled environmental conditions. We have conducted molecular dynamics simulation on a class of corannulene-based molecules to demonstrate the characteristics of self-assembly and to aid in the design of the molecular subunits. The edge complementarities can be of diverse structure, and they need not reflect the fivefold symmetry of the molecular core. Thus, self-assembling capsids formed from coded subunits can serve as addressable nanocontainers or custom-made structural elements.corannulene ͉ icosahedral capsids ͉ molecular containers ͉ physical modeling ͉ nanotechnology

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Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 99%

Chemical mimicry of viral capsid self-assembly

Olson

Keinan

2007

Proc. Natl. Acad. Sci. U.S.A.

102

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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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“…The bowl-shaped structure of corannulene (C 20 H 10 ) is well known, and we have adopted similar structural parameters to those reported in previous theoretical and experimental work [37]. The optimized structures and corresponding geometrical parameters of corannulene are shown in Figure 1.…”

Section: Equilibrium Geometriesmentioning

confidence: 99%

DFT study on nonlinear optical properties of lithium-doped corannulene

Jiang

Liu

et al. 2012

Chin. Sci. Bull.

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The effects of lithium doping on the nonlinear optical properties of new electrodes (lithium-doped corannulene) were investigated in detail. Nine dynamically stable geometries of Li n -C 20 H 10 (n=1, 2) are predicted by B3LYP/6-31G (d,p). Among these nine structures, the largest first static hyperpolarizability ( 0 ) is computed to be 15314 au, which is dramatically larger than the  0 value of 74 au for C 20 H 10 , indicating that Li doping plays an important role in elevating the first hyperpolarizability of corannulene. The extensive number of works that have been performed over the past two decades to investigate the nonlinear optical (NLO) properties of novel NLO materials [1][2][3][4][5][6][7] have been devoted to discovering the important/key influencing factors that can lead to dramatic increases in the first hyperpolarizability [8]. The strategies used mainly focused on utilizing molecules that contain extended -electron systems [9] or that can be characterized as planar donor--conjugated bridge-acceptor (D--A) types [10,11] [29]. Corannulene can be thought of as the upper third of a C 60 molecule with the valences of the outermost atoms saturated by H atoms. The molecule resembles a shallow bowl with C 5v symmetry (Figure 1) and the six-membered rings at the periphery lie significantly out of the plane. C 20 H 10 exhibits a number of interesting properties [30,31] and its complexes with ions or atoms, such as alkaline cations or transition metal atoms [32][33][34][35], have been studied both experimentally and theoretically. Following the discussion above, we investigated corannulene molecules with Li doping for the design of novel NLO materials.In the current work, to investigate the effect of Li doping on the NLO properties of corannulene, we predict the structural and electronic properties of Li n -C 20 H 10 (n=1, 2) at the atomic level. It is found that the large hyperpolarizabilities of Li n -C 20 H 10 (n=1, 2) strongly depend upon the concentration and position of the Li atoms.

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X-ray Quality Geometries of Geodesic Polyarenes from Theoretical Calculations: What Levels of Theory Are Reliable?

Cited by 197 publications

References 15 publications

Chemical mimicry of viral capsid self-assembly

Chemical mimicry of viral capsid self-assembly

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

DFT study on nonlinear optical properties of lithium-doped corannulene

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X-ray Quality Geometries of Geodesic Polyarenes from Theoretical Calculations: What Levels of Theory Are Reliable?

Cited by 197 publications

References 15 publications

Chemical mimicry of viral capsid self-assembly

Chemical mimicry of viral capsid self-assembly

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

DFT study on nonlinear optical properties of lithium-doped corannulene

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Product

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