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Feeding a Molecular Squid: A Pliable Nanocarbon Receptor for Electron-Poor Aromatics
journal contribution
posted on 2020-08-28, 22:44 authored by Rafał Frydrych, Tadeusz Lis, Wojciech Bury, Joanna Cybińska, Marcin StępieńA hybrid nanocarbon receptor consisting of a calix[4]arene and
a bent oligophenylene loop (“molecular squid”),
was obtained in an efficient, scalable synthesis. The system contains
an electron-rich cavity with an adaptable shape, which can serve as
a host for electron deficient guests, such as diquat, 10-methylacridinium,
and anthraquinone. The new receptor forms inclusion complexes
in the solid state and in solution, showing a dependence of the observed
binding strength on the shape of the guest species and its charge.
The interaction with the methylacridinium cation in solution
was interpreted in terms of a 2:1 binding model, with K11 = 5.92(7) × 103 M–1. The solid receptor is porous to gases and vapors, yielding an uptake
of ca. 4 mmol/g for methanol at 293 K. In solution, the receptor shows
cyan fluorescence (λmaxem = 485 nm, ΦF = 33%), which is partly quenched upon binding of guests.
Methylacridinium and anthraquinone adducts show red-shifted
emission in the solid state, attributable to the charge-transfer character
of these inclusion complexes.