Rationally Designed Calix[4]arene–Pyrrolotetrathiafulvalene Receptors for Electron-Deficient Neutral Guests

Abstract

Four upper rim bis-monopyrrolotetrathiafulvalene-calix[4]arene conjugates 2a,b and 3a,b have been efficiently synthesized using a modular construction approach. The new compounds feature a molecular tweezer architecture with a quasi-parallel arrangement of redox-active tetrathiafulvalene (TTF) arms, which serve as the guest binding centers. Complexation studies using UV/vis binding titrations revealed a high affinity of the calixarene-TTF receptors for planar electron-deficient guests, leading to formation of deeply colored charge-transfer complexes in solution. The binding efficiency of the receptors depends on the flexibility of the calixarene scaffolds and the electronic nature of the TTF arms: the highest binding efficiency is shown by receptor 2b, featuring a highly preorganized molecular structure and an electron-rich TTF moiety.