The Hunter Falls Prey: Photoinduced Oxidation of C₆₀ in Inclusion Complex with Perfluorocycloparaphenylene

Abstract

Perfluorocycloparaphenylenes (PFCPPs) are cycloparaphenylenes (CPPs) in which all hydrogen atoms have been replaced by fluorine atoms. Like CPPs, PFCPPs are highly strained, hoop‐shaped π‐conjugated molecules. In this article, we report a computational modeling of photoinduced electron transfer processes in the inclusion complex of PF[10]CPP with C60 fullerene. Its unique feature is the favorable electron transfer from C60 to the host molecule. The photooxidation of C60 is predicted to occur on a sub‐nanosecond timescale. The PF[10]CPP⊃C60 dyad is the first nanoring‐fullerene complex in which C60 acts as an electron donor in the photoinduced charge separation.

Aromaticity controls the excited-state properties of host–guest complexes of nanohoops

“…However, it is known that for fullerene complexes with symmetric CPPs and their π-extended analogs the solvation energy of CT states does not differ much from the energy of GS. 64,65 The obtained results show that the difference in dipole moments between CT1 and GS states in [4]DHPP⊃C 60 does not exceed 2 D. Consequently, the solvation energy of the CT1 state is −0.91 eV. Detailed solvation data in DCM are given in Table S7, ESI †.…”

“…There are only a few reports, in which fullerene has been used as an electron donor in combination with strong electron acceptors. Among them, the complexes with trinitrofluorenone, 67 subphthalocyanines, 68 and xanthylium 69 shows intramolecular PET, whereas complexes with p -chloranil 70 and [10]-perfluorocycloparaphenylene 65 are the rare examples of intermolecular PET from fullerene to strong electron acceptor.…”

Half-substituted fluorocycloparaphenylenes with high symmetry: Synthesis, properties and derivatization to densely substituted carbon nanorings

“…In recent years, fluorinated CPPs (FCPPs) have attracted much attention as electron-accepting CPPs as well as strained fluoroarenes. Herein, we report the synthesis, properties, and derivatization of novel FCPPs; F16 [8]CPP (1) and F12 [6]CPP (2), in which ortho-difluorophenylene units are circularly connected to form CPP structure. The short-step synthesis of 1 and 2 has been achieved by the strategy using macrocyclic nickel or gold complexes.…”

“…The short-step synthesis of 1 and 2 has been achieved by the strategy using macrocyclic nickel or gold complexes. Furthermore, the derivatization of 1 was successfully achieved to afford a new heteroring-containing carbon nanoring; hexadecapyrrolyl [8]cycloparaphenylene 5, where 16 pyrrole rings are densely substituted on CPP framework.…”

“…Among CPP families, fluorinated CPPs (FCPPs) represent recent hot targets since they are not only new substituted CPPs but also rarely synthesized strained fluoroarenes (Figure 1b). [7][8][9] In 2018, the group of Yamago has opened the chemistry of FCPPs by the synthesis of partially fluorinated CPPs (parFCPPs), F8 [6]CPP and F12 [9]CPP through the formation of macrocyclic Pt complexes followed by reductive aromatization of tetrafluorocyclohexadiene units. [10] Jasti and coworkers also reported the synthesis of parFCPPs, F8 [10]CPP, F8 [12]CPP and F12 [12]CPP, via tetrafluorobenzene and cyclohexadiene moieties containing macrocycle.…”