Chrysene-Bridged Porphyrin Tweezers: Chiral Receptors for Fullerenes

Shigeki Mori; Naoki Kawamoto; Hidemitsu Uno

doi:10.1002/cplu.201900046

Chrysene-Bridged Porphyrin Tweezers: Chiral Receptors for Fullerenes

Chempluschem. 2019 Jun;84(6):686-693. doi: 10.1002/cplu.201900046. Epub 2019 Apr 4.

Authors

Shigeki Mori¹, Naoki Kawamoto², Hidemitsu Uno²

Affiliations

¹ Division of Material Science, Advanced Research Support Center, Ehime University, 2-5 Bunkyo-cho, Matsuyama, 790-8577, Japan.
² Department of Chemistry and Biology Graduate School of Science and Engineering, Ehime University, 2-5 Bunkyo-cho, Matsuyama, 790-8577, Japan.

PMID: 31944003
DOI: 10.1002/cplu.201900046

Abstract

Bis(bicyclic) molecules dimethanochrysene and diethanochrysene were prepared by Diels-Alder reaction of the naphthodiyne equivalent with cyclopentadiene and 1,3-cyclohexadiene, respectively. Reaction of dimethanochrysene and 7,9-diphenyl-8H-cyclopent[a]acenaphthylen-8-one resulted in the generation of a fluorescent hydrocarbon in unexpected multistep pericyclic reactions. Syn-oriented diethanochrysene-connected bisporphyrin tweezers was prepared from the reaction of chrysene-bridged syn-dipyrrole with tripyrranedicarbaldehyde. The structure of the receptor and its 1 : 1 complex with C₆₀ or C₇₀ was determined by X-ray diffraction analysis. The dihedral angles of the bicyclo[2.2.2]octadiene moieties were narrowed by complexation of the receptor with the fullerenes. The binding affinities of the tweezers with C₆₀ and C₇₀ were calculated to be 2.7(4)×10⁴ and 8.01(7)×10⁴ M^-1 , respectively by UV-vis and fluorescence spectroscopy.

Keywords: chrysene; fullerenes; host-guest chemistry; molecular tweezers; porphyrins.

Publication types

Research Support, Non-U.S. Gov't