Saturnene Revealed: X‐ray Crystal Structure of D5d‐C60F20 Formed in Reactions of C60 with AxMFy Fluorinating Agents (A=Alkali Metal; M=3d Metal)

Shustova, Natalia B.; Mazej, Zoran; Chen, Yu‐Sheng; Popov, Alexey A.; Strauss, Steven H.; Boltalina, Olga V.

doi:10.1002/ange.200905832

Cited by 4 publications

(4 citation statements)

References 30 publications

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“…Adding substituents onto C 60 to obtain chemically stable, IAP-obeying fluorofullerene structures has been experimentally realized. For example, C 60 F 18 has a patch of 2 and a fullerene hemisphere; C 60 F 20 has two patches of 3 ; C 60 F 36 has four patches of 2 , three patches of 2 , and one patch of 1 ; C 60 F 44 has eight patches of 1 ; and C 60 F 48 has six patches of 1 . All these fluorofullerene structures have been unambiguously characterized by experiments.…”

Section: Resultsmentioning

confidence: 92%

Improved Description for the Structures of Fullerenols C₆₀(OH)_n (n = 12–48) and C_2v(9)-C₈₂(OH)_x (x = 14–58)

et al. 2016

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Highest occupied molecular orbital–lowest unoccupied molecular orbital (H-L) energy gaps govern the chemical stabilities of molecules. Molecules with larger H-L gaps are more inert to chemical reactions and thus more experimentally separable. In this sense, H-L gaps play a more important role than energies of formation in determining the structures of the fullerenols that can be experimentally isolated. However, previous structural predictions for fullerenols are mainly based on energies. Recently, we proposed a rule of chemical stability for multiple addition products of fullerenes and endohedral metallofullerenes. In this study, we implement this rule into a computer program and use it to automatically determine large-energy-gap structures for C60 and C82 fullerenols. C60(OH) n (n = 12–48) and C 2v (9)-C82(OH) x (x = 14–58) fullerenols have been studied using this program. All the structures determined have H-L gaps larger than those predicted previously. Some of the structures simultaneously have even more favorable thermodynamic stabilities than the previously predicted structures. Therefore, the results we present here provide an improved description for the structures of fullerenols.

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Section: Resultsmentioning

confidence: 92%

Improved Description for the Structures of Fullerenols C₆₀(OH)_n (n = 12–48) and C_2v(9)-C₈₂(OH)_x (x = 14–58)

et al. 2016

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“…For instance, multiple additions to a fullerene cage in a one‐pot reaction could result in a high degree of fullerene derivatization. Indeed, there are fullerene‐based compounds which contain 18, 20, or even more than 40 groups on the carbon cage . Furthermore, fullerene derivatives with a close number of addends (e.g., 10, 12, or 14) or the same number of groups but with different addition patterns (i.e., different position of the groups on the carbon sphere) possess very similar physicochemical properties, which also impede their separation .…”

Section: Methodsmentioning

confidence: 99%

Fulleretic Well‐Defined Scaffolds: Donor–Fullerene Alignment Through Metal Coordination and Its Effect on Photophysics

et al. 2016

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Herein, we report the first example of ac rystalline metal-donor-fullerene framework, in which control of the donor-fullerene mutual orientation was achieved through chemical bond formation, in particular,bymetal coordination. The 13 Cc ross-polarization magic-angle spinning NMR spectroscopy, X-rayd iffraction, and time-resolved fluorescence spectroscopyw ere performed for comprehensive structural analysis and energy-transfer (ET) studies of the fulleretic donor-acceptor scaffold. Furthermore,i nc ombination with photoluminescence measurements,t he theoretical calculations of the spectral overlap function, Fçrster radius,e xcitation energies,a nd band structure were employed to elucidate the photophysical and ET processes in the prepared fulleretic material. We envision that the well-defined fulleretic donoracceptor materials could contribute not only to the basic science of fullerene chemistry but would also be used towards effective development of organic photovoltaics and molecular electronics.The success of fullerenes and their derivatives in engineering organic photovoltaics and molecular electronics is mainly owed to their electron-accepting properties and ultrafast electron/energy transfer. [1,2] As previously demonstrated, fullerene(acceptor)-donor alignment could significantly affect excitonic device performance.F or instance,t he arrangement of the donor fullerene is crucial for efficient energy/charge transfer, because of possible effects on the distance of exciton diffusion, p-p stacking, or Fçrster radius (resonance energy transfer). As ar esult, formation of fullerene stacks led to an enhancement of solar cell efficiency,in contrast to non-stacking fullerene derivatives. [3] There are few known reports of spatial organization of graphitic crystalline materials through the covalent linkage of fullerene derivatives. [4][5][6][7][8] Moreover,the known approaches for fulleretic material organization are mainly based on immobilization of the fullerenes inside porous matrices possessing alarge aperture. [9][10][11] There are very few reports of crystalline fullerene-metal-coordinated extended structures. [12][13][14][15] Furthermore,n one of these studies explore the concept demonstrated herein, which tackles the development of an ovel crystalline metal-donor-acceptor framework, in which control of the mutual orientation of the donor and fullerenebased acceptor was achieved through chemical bond formation, that is,m etal coordination. Despite the tremendous interest in self-assemblies (in particular,c oordination polymers such as covalent or metal-organic frameworks;COFs or MOFs) [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] and fullerene chemistry,t ot he best of our knowledge the prepared metal-organic fullerene-containing framework is the first example of ac rystalline hybridextended structure,inw hich control over mutual orientation of both donor and fullerene-based acceptor is achieved through metal coordination (Scheme 1). Scheme 1. As chematic representation of organizatio...

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“…The closed equatorial loop of chlorine atoms cuts its π-system into the two corannulene caps. Previously, a double corannulene structure has been observed in the IPR C 60 F 20 ("saturnene") 42 and the first discovered non-IPR chloride 271 C 50 Cl 10. 22 Also to be mentioned in this regard are 18917 C 76 Cl 24 , a considerably flattened molecule with two vinylcoronene substructures, 7,8 and the recent nonclassical C 78 (NC2)Cl 24 , also flattened and with a single closed loop of chlorines.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

“…With less bulky chlorine addends and more FPPs, the thermodynamic driving force is, expectedly, much higher: 1810 C 60 Cl 24 (1) and 1805 C 60 Cl 24 (2) with four FPPs are, respectively, 267 and 336 kJ mol −1 more stable than the IPR compound T d -C 60 Cl 24 . 45 For structure 3 with five FPPs, no direct IPR counterpart is presently known, but compared to a hypothetical IPR D 5d -C 60 Cl 20 , an analogue of saturnene C 60 F 20 with the same closed loop addition pattern, 42 The need for higher temperatures to trigger skeletal rearrangements in buckminsterfullerene gives rise to a question, whether the I h -C 60 cage is harder to transform in itself, or other effects are possibly implicated. The most obvious is the effect of the chlorination motif.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

Rebuilding C₆₀: Chlorination-Promoted Transformations of the Buckminsterfullerene into Pentagon-Fused C₆₀ Derivatives

et al. 2018

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In recent years, many higher fullerenes that obey the isolated pentagon rule (IPR) were found capable of rearranging into molecules with adjacent pentagons and even with heptagons via chlorination-promoted skeletal transformations. However, the key fullerene, buckminsterfullerene I -C, long seemed insusceptible to such rearrangements. Now we demonstrate that buckminsterfullerene yet can be transformed by chlorination with SbCl at 420-440 °C and report X-ray structures for the thus-obtained library of non-IPR derivatives. The most remarkable of them are non-IPR CCl and CCl with fundamentally rearranged carbon skeletons featuring, respectively, four and five fused pentagon pairs (FPPs). Further high-temperature trifluoromethylation of the chlorinated mixture afforded additional non-IPR derivatives C(CF) and C(CF), both with two FPPs, and a nonclassical C(CF)F with a heptagon, two FPPs, and a fully fused pentagon triple. We discuss the general features of the addition patterns in the new non-IPR compounds and probable pathways of their formation via successive Stone-Wales rearrangements.

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Saturnene Revealed: X‐ray Crystal Structure of D_5d‐C₆₀F₂₀ Formed in Reactions of C₆₀ with A_xMF_y Fluorinating Agents (A=Alkali Metal; M=3d Metal)

Cited by 4 publications

References 30 publications

Improved Description for the Structures of Fullerenols C₆₀(OH)_n (n = 12–48) and C_2v(9)-C₈₂(OH)_x (x = 14–58)

Improved Description for the Structures of Fullerenols C₆₀(OH)_n (n = 12–48) and C_2v(9)-C₈₂(OH)_x (x = 14–58)

Fulleretic Well‐Defined Scaffolds: Donor–Fullerene Alignment Through Metal Coordination and Its Effect on Photophysics

Rebuilding C₆₀: Chlorination-Promoted Transformations of the Buckminsterfullerene into Pentagon-Fused C₆₀ Derivatives

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Saturnene Revealed: X‐ray Crystal Structure of D5d‐C60F20 Formed in Reactions of C60 with AxMFy Fluorinating Agents (A=Alkali Metal; M=3d Metal)

Cited by 4 publications

References 30 publications

Improved Description for the Structures of Fullerenols C60(OH)n (n = 12–48) and C2v(9)-C82(OH)x (x = 14–58)

Improved Description for the Structures of Fullerenols C60(OH)n (n = 12–48) and C2v(9)-C82(OH)x (x = 14–58)

Fulleretic Well‐Defined Scaffolds: Donor–Fullerene Alignment Through Metal Coordination and Its Effect on Photophysics

Rebuilding C60: Chlorination-Promoted Transformations of the Buckminsterfullerene into Pentagon-Fused C60 Derivatives

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Saturnene Revealed: X‐ray Crystal Structure of D_5d‐C₆₀F₂₀ Formed in Reactions of C₆₀ with A_xMF_y Fluorinating Agents (A=Alkali Metal; M=3d Metal)

Improved Description for the Structures of Fullerenols C₆₀(OH)_n (n = 12–48) and C_2v(9)-C₈₂(OH)_x (x = 14–58)

Improved Description for the Structures of Fullerenols C₆₀(OH)_n (n = 12–48) and C_2v(9)-C₈₂(OH)_x (x = 14–58)

Rebuilding C₆₀: Chlorination-Promoted Transformations of the Buckminsterfullerene into Pentagon-Fused C₆₀ Derivatives