A theoretical study on the interaction between well curved conjugated systems and fullerenes smaller than C60 or larger than C70. (9th October 2014)

• Record Type: Journal Article
• Authors: Denis, Pablo A.
• Is Part Of: Journal of physical organic chemistry. Volume 27:Number 12(2014:Dec.)
• Page Start: 918
• Page End: 925
• Publication Date: 2014-10-09
• Subjects: Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3357
• Languages: English
• ISSNs: 0894-3230

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>A large body of data exists about the interaction between curved π systems and C<sub>60</sub> or C<sub>70</sub>. However, little is known about the interaction with fullerenes smaller than C<sub>60</sub> or larger than C<sub>70</sub>. To fill that gap, we studied, by means of density functional theory (M06‐2X), the interaction between corannulene, pentaindenocorannulene, C<sub>60</sub>H<sub>28</sub> buckycatcher and the following fullerenes: C<sub>44</sub>, C<sub>50</sub>, C<sub>80</sub>, C<sub>90</sub>, C<sub>100</sub>, C<sub>180</sub> and C<sub>240</sub>. For fullerenes smaller than C<sub>60</sub>, their high reactivity facilitated the covalent addition to the hosts assayed. Yet, the reaction energies determined for the covalent addition were comparable to those calculated for the formation of supramolecular complexes. Thus, the receptor may host a fullerene and at least have another one attached. As expected, for fullerenes larger than C<sub>70</sub>, supramolecular complexes were preferred over covalent assemblies. The binding energies with bowls increased with the size of the fullerenes in a non‐monotonic fashion since they depended on the shape of the fullerene. Indeed, for one C<sub>80</sub> isomer, it is possible to find a region which forms a complex with corannulene that is stronger than C<sub>60</sub>@corannulene, while another region exists whose interaction with corannulene is weaker. As the size of the fullerene becomes larger, ball–socket interactions are weakened, and CH–π interactions become important, accounting for the large interaction determined for corannulene and graphene. Finally, for the buckycatcher, the maximum encapsulation energy among the fullerenes assayed was displayed by C<sub>90</sub>. The fullerenes C<sub>80</sub>, C<sub>90</sub> and C<sub>100</sub> formed complexes with the buckycatcher which are stronger than in C<sub>60</sub>@buckycatcher. Copyright © 2014 John Wiley & Sons, Ltd.</p> </abstract>