Influence of the Encapsulated Clusters on the Electrochemical Behaviour of Endohedral Fullerene Derivatives: Comparative Study of N‐Tritylpyrrolidino Derivatives of Sc3N@Ih‐C80 and Lu3N@Ih‐C80

Chen, Ning; Pinzón, Julio R.; Echegoyen, Luís

doi:10.1002/cphc.201001015

Cited by 19 publications

(27 citation statements)

References 30 publications

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“…This fact also agrees with different reduction behavior of [6,6] adducts of Sc 3 N@C 80 , on the one hand, and all other M 3 N@C 80 , on the other hand. 25 Concluding Remarks. In this work, using DFT theory, we have studied in detail dimerization of the anion-radical of NCFs to find if formation of the dimers can be an explanation of the irreversible reduction steps exhibiting by these compounds.…”

Section: Lettermentioning

confidence: 98%

Dimerization of Radical-Anions: Nitride Clusterfullerenes versus Empty Fullerenes

Popov

Avdoshenko

Cuniberti

et al. 2011

J. Phys. Chem. Lett.

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b S Supporting InformationO ne of the important properties of fullerenes for their broad applications is the ease with which they can accept electrons. Endohedral metallofullerenes, and, in particular, nitride clusterfullerenes (NCFs) also exhibit such properties 1À3 (gasphase electron affinity of Sc 3 N@C 80 is even higher than that of C 60 4 ). Moreover, in a number of recent studies, NCFs have been shown to be superior to C 60 in photovoltaic applications. 5À8 Despite the importance of the electron transfer reactions of NCFs in this context, there is still a challenging question that has not been clearly understood up to now. Whereas empty fullerenes exhibit perfectly reversible reduction steps in solution at room temperature, the majority of NCFs exhibit irreversible reduction behavior at standard voltammetric scan rates. 9À17 For Sc 3 N@C 80 , Echegoyen has shown that electrochemical reversibility can be reached at fast scan rates (5 V/s was reported for the first reduction step). 9 Extended studies of Dy 3 N@C 78 and Dy 3 N@C 80 have shown that for these NCFs electrochemically reversible reductions were not achieved up to the scan rates of 80 V/s. 14 Likewise, irreversible reduction steps are also observed for Sc 3 N@C 68 , 15 Sc 3 N@C 78 , 18 and a series of M 3 N@C 2n (M = lanthanide), 2 the only exclusion from this rule being M 3 N@C 88 , which exhibited reversible reductions. 17 Dedicated studies have shown that despite electrochemical irreversibility, reduction steps of NCFs are chemically reversible. 9,10,14 That is, the followup reaction accompanying electron transfer is reversible and pristine NCFs can be recovered at the end of a voltammetric cycle. Thus, irreversible reactions with the solvent and the sample decomposition can be excluded. (This was shown by multiple cycling as well as mass-spectrometric studies of the electrolysis products, which showed no traces of NCFs' derivatives.) To explain this peculiar reduction behavior of NCFs, we suggested a double-square schema in which structural rearrangement of the cluster (e.g., pyramidalization) in radical anions was proposed; 14,16 however, the nature of this rearrangement remained unclear. Extended theoretical studies of the charged NCFs did not reveal any structural changes that might be responsible for the irreversibility of electrochemical reduction. 19À22 Chemical derivatization of NCFs also changes their electrochemical properties. It was shown that trifluoromethylated Sc 3 N@C 80 derivatives tend to exhibit electrochemically reversible reduction steps. For Sc 3 N@C 80 (CF 3 ) 2 , three reversible reduction steps have been observed, and stability of the radical ABSTRACT: In contrast with empty fullerenes, nitride clusterfullerenes usually exhibit irreversible reduction steps at moderate electrochemical scan rates. However, these reduction steps are chemically reversible, indicating that reversible follow-up reaction takes place. To explain this phenomenon, we analyze in this work if anion-radicals of nitride clusterfullerenes are more pro...

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Section: Lettermentioning

confidence: 98%

Dimerization of Radical-Anions: Nitride Clusterfullerenes versus Empty Fullerenes

Popov

Avdoshenko

Cuniberti

et al. 2011

J. Phys. Chem. Lett.

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“…Therefore, substantial [6,6] to [5,6] isomerization of adducts should occur during the addition of azomethine ylides to Sc 3 N@ I h ‐C 80 . To the best of our knowledge, the isolation of the [6,6]‐pyrrolidino adduct of Sc 3 N@ I h ‐C 80 has been limited to synthesis through the cycloaddition of N ‐tritylazomethine ylide ,…”

Section: Introductionmentioning

confidence: 99%

Preparation, Structural Determination, and Characterization of Electronic Properties of [5,6]‐ and [6,6]‐Carbosilylated Sc₃N@I_h‐C₈₀

Kako

Sugiura

Miyabe

et al. 2017

Chemistry An Asian Journal

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Photochemical carbosilylation of Sc N@I -C with silirane 1 afforded two corresponding [5,6]-adducts, 2 and 3, and a [6,6]-adduct, 4. The structural and electronic properties of these products were characterized by means of spectroscopic, electrochemical, and theoretical methods. The structure of 2 was disclosed by means of single-crystal X-ray crystallographic analysis. Thermal isomerization of 3 to 2 was observed, whereas that of 2 to 3 proceeded less efficiently at 100 °C. Upon heating under the same conditions, adduct 4 underwent facile decomposition to afford Sc N@I -C , or isomerized into small amounts of 2 and 3. The relative stabilities of 2, 3, and 4 were rationalized through the results of theoretical calculations. In contrast, adducts 2, 3, and 4 were stable under the photolytic conditions employed for carbosilylation. The photochemical functionalization of Sc N@I -C represents a convenient synthetic method to obtain thermally labile fullerene-based products.

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“…Herein, we report the carbosilylation of Lu 3 N@ I h -C 80 via photoreactions using siliranes 1 [ 21 ] and 2 [ 22 ] to afford the corresponding [5,6]- and [6,6]-adducts. The electronic effect of silirane addition on Lu 3 N@ I h -C 80 is discussed in comparison with that of the 1,3-dipolar addition of azomethine ylides [ 23 , 24 ].…”

Section: Introductionmentioning

confidence: 99%

Photoreactions of Endohedral Metallofullerene with Siliranes: Electronic Properties of Carbosilylated Lu3N@Ih-C80

et al. 2017

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Photochemical carbosilylation of Lu3N@Ih-C80 was performed using siliranes (silacyclopropanes) to afford the corresponding [5,6]- and [6,6]-adducts. Electrochemical studies indicated that the redox potentials of the carbosilylated derivatives were shifted cathodically in comparison with those of the [5,6]-pyrrolidino adducts. The electronic effect of the silirane addends on Lu3N@Ih-C80 was verified on the basis of density functional theory calculations.

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Influence of the Encapsulated Clusters on the Electrochemical Behaviour of Endohedral Fullerene Derivatives: Comparative Study of N‐Tritylpyrrolidino Derivatives of Sc₃N@I_h‐C₈₀ and Lu₃N@I_h‐C₈₀

Cited by 19 publications

References 30 publications

Dimerization of Radical-Anions: Nitride Clusterfullerenes versus Empty Fullerenes

Dimerization of Radical-Anions: Nitride Clusterfullerenes versus Empty Fullerenes

Preparation, Structural Determination, and Characterization of Electronic Properties of [5,6]‐ and [6,6]‐Carbosilylated Sc₃N@I_h‐C₈₀

Photoreactions of Endohedral Metallofullerene with Siliranes: Electronic Properties of Carbosilylated Lu3N@Ih-C80

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Influence of the Encapsulated Clusters on the Electrochemical Behaviour of Endohedral Fullerene Derivatives: Comparative Study of N‐Tritylpyrrolidino Derivatives of Sc3N@Ih‐C80 and Lu3N@Ih‐C80

Cited by 19 publications

References 30 publications

Dimerization of Radical-Anions: Nitride Clusterfullerenes versus Empty Fullerenes

Dimerization of Radical-Anions: Nitride Clusterfullerenes versus Empty Fullerenes

Preparation, Structural Determination, and Characterization of Electronic Properties of [5,6]‐ and [6,6]‐Carbosilylated Sc3N@Ih‐C80

Photoreactions of Endohedral Metallofullerene with Siliranes: Electronic Properties of Carbosilylated Lu3N@Ih-C80

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Influence of the Encapsulated Clusters on the Electrochemical Behaviour of Endohedral Fullerene Derivatives: Comparative Study of N‐Tritylpyrrolidino Derivatives of Sc₃N@I_h‐C₈₀ and Lu₃N@I_h‐C₈₀

Preparation, Structural Determination, and Characterization of Electronic Properties of [5,6]‐ and [6,6]‐Carbosilylated Sc₃N@I_h‐C₈₀