Unusual multistep reaction of C70Cl10 with thiols producing C70[SR]5H

Khakina, Ekaterina A.; Peregudov, Аlexander S.; Yurkova, Anastasiya A.; Piven, Natalya P.; Shestakov, Alexander F.; Troshin, Pavel A.

doi:10.1016/j.tetlet.2016.01.066

Cited by 11 publications

(4 citation statements)

References 31 publications

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“…Alternatively, the functionalization of fullerenes can be achieved by attaching chemical groups to the cage outer surface, leading to the so-called exohedral fullerenes. ,, The exohedral derivatization of fullerenes can enhance their solubility and proccessibility and endow them with novel properties . Generally speaking, the functional groups can be any chemical species, from simple atoms, such as hydrogen − or halogens, − to very complex moieties, such as sugars , and macrocycles. , Therefore, exohedral fullerenes have numerous applications in medicine − and materials science. − Here, we put special emphasis on fullerenes functionalized by atoms or simple groups (hereafter referred to as prototype exohedral fullerenes), which are the starting point for much more complex derivatives and the building blocks of supramolecular fullerene polymers and networks. , Hydrogenated fullerenes or fulleranes have been detected in samples of the Allende meteorite and are probably carriers of diffuse interstellar bands and other interstellar and circumstellar features. , The hydrogenation of fullerenes may also have important implications for catalysts, hydrogen storage, and electronic devices. ,− Halogenated fullerenes can be conveniently used in organic synthesis of more complex fullerene derivatives, for they are precursors for subsequent nucleophilic substitution or addition at free sites elsewhere in the molecule. − The enhanced electron affinity makes halogenated fullerenes excellent electron acceptors for novel charge-transfer complexes, donor–acceptor dyads, , and photonic/photovoltaic devices. , Perfluoroalkylated fullerenes have also been intensively studied, with practical applications as powerful and tunable acceptors in the field of organic electronics. − …”

Section: Introductionmentioning

confidence: 99%

Topology-Based Approach to Predict Relative Stabilities of Charged and Functionalized Fullerenes

Wang

Díaz‐Tendero

Alcamı́

et al. 2018

J. Chem. Theory Comput.

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Understanding the relationship between structure and stability is one of the fundamental aspects of fullerene chemistry, as the number of possible cage isomers is very large and complexity increases by orders of magnitude when chemical groups are attached to the fullerene cage. The well-established stability rules valid for neutral fullerenes do not apply to many charged or functionalized fullerenes. Here we present the theory, implementation, and applications of two simple topology-based models that allow one to predict the relative stability of charged and functionalized fullerenes without the need for quantum chemistry calculations: (i) the charge stabilization index (CSI) model, based on the concepts of cage connectivity and frontier π orbitals, which offers a general framework for the relative stability of both positively and negatively charged fullerenes, as well as endohedral metallofullerenes, and (ii) the exohedral fullerene stabilization index (XSI) model, which incorporates all key factors governing the stability of exohedral fullerenes, namely, π delocalization, σ strain, and steric hindrance between addends. Based exclusively on topological information, both models are powerful prescreening tools for predicting the most stable structures of a large number of charged and functionalized fullerenes. For easy use by fullerene chemists, both models have been implemented in the FullFun (for Fullerene Functionalization) software package, whose effectiveness and efficiency are demonstrated by some illustrative examples.

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Section: Introductionmentioning

confidence: 99%

Topology-Based Approach to Predict Relative Stabilities of Charged and Functionalized Fullerenes

Wang

Díaz‐Tendero

Alcamı́

et al. 2018

J. Chem. Theory Comput.

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“…The exhohedral fullerenes thus produced, hereafter called prototype exohedral fullerenes, are found in many areas of science and have themselves interesting properties that are relevant to many applications . Halogenated exohedral fullerenes, for instance, allow for nucleophilic substitution or addition of chemical species at specific fullerene sites − with a selectivity that is difficult to achieve in pristine fullerenes. Fluorofullerenes are known to have variable optical gaps and, therefore, are ideal to produce selective light absorbers. ,,, They have also been used as dopants to improve the surface conductivity of diamond and as components of cathode materials for lithium batteries. , The simplest of all prototype exohedral fullerenes, hydrogenated fullerenes or fulleranes, are considered as potential carriers of diffuse interstellar bands and other interstellar and circumstellar features , and have been detected in meteorites …”

Section: Introductionmentioning

confidence: 99%

Relative Stability of Empty Exohedral Fullerenes: π Delocalization versus Strain and Steric Hindrance

et al. 2017

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Predicting and understanding the relative stability of exohedral fullerenes is an important aspect of fullerene chemistry, since the experimentally formed structures do not generally follow the rules that govern addition reactions or the making of pristine fullerenes. First-principles theoretical calculations are of limited applicability due to the large number of possible isomeric forms, for example, more than 50 billion for CX. Here we propose a simple model, exclusively based on topological arguments, that allows one to predict the relative stability of exohedral fullerenes without the need for electronic structure calculations or geometry optimizations. The model incorporates the effects of π delocalization, cage strain, and steric hindrance. We show that the subtle interplay between these three factors is responsible for (i) the formation of non-IPR (isolated pentagon rule) exohedral fullerenes in contrast with their pristine fullerene counterparts, (ii) the appearance of more pentagon-pentagon adjacencies than predicted by the PAPR (pentagon-adjacency penalty rule), (iii) the changes in regioisomer stability due to the chemical nature of the addends, and (iv) the variations in fullerene cage stability with the progressive addition of chemical species.

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“…The thiolation of fullerenes is rarely studied [ 64 , 65 ]. Thiolation with thiols is typically achieved via a reaction with multiple chlorinated fullerenes [ 66 , 67 ]. Recently, the thiolation of C 60 with thiols conjugated to polystyrene was reported [ 68 ].…”

Section: The Methods Of Functionalization Of Fullerenesmentioning

confidence: 99%

Functionalized Fullerenes and Their Applications in Electrochemistry, Solar Cells, and Nanoelectronics

et al. 2023

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Carbon-based nanomaterials have rapidly advanced over the last few decades. Fullerenes, carbon nanotubes, graphene and its derivatives, graphene oxide, nanodiamonds, and carbon-based quantum dots have been developed and intensively studied. Among them, fullerenes have attracted increasing research attention due to their unique chemical and physical properties, which have great potential in a wide range of applications. In this article, we offer a comprehensive review of recent progress in the synthesis and the chemical and physical properties of fullerenes and related composites. The review begins with the introduction of various methods for the synthesis of functionalized fullerenes. A discussion then follows on their chemical and physical properties. Thereafter, various intriguing applications, such as using carbon nanotubes as nanoreactors for fullerene chemical reactions, are highlighted. Finally, this review concludes with a summary of future research, major challenges to be met, and possible solutions.

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Unusual multistep reaction of C70Cl10 with thiols producing C70[SR]5H

Cited by 11 publications

References 31 publications

Topology-Based Approach to Predict Relative Stabilities of Charged and Functionalized Fullerenes

Topology-Based Approach to Predict Relative Stabilities of Charged and Functionalized Fullerenes

Relative Stability of Empty Exohedral Fullerenes: π Delocalization versus Strain and Steric Hindrance

Functionalized Fullerenes and Their Applications in Electrochemistry, Solar Cells, and Nanoelectronics

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