A Macrocycle/Molecular‐Clip Complex that Functions as a Quadruply Controllable Molecular Switch

Abstract

Herein, we report the synthesis of a molecular clip with TTF side-walls and its binding behavior towards electron-deficient guests, namely the formation of macrocycle/molecular-clip supramolecular complexes in solution. Four different sets of external stimuli--the K(+)/[2.2.2]cryptand, NH(4) (+)/Et(3)N and (p-BrPh)(3)NSbCl(6)/Zn pairs, and heating/cooling cycles-control the movement of this molecular switch between its threaded and unthreaded states and provide color changes that are observable by the naked eye. This macrocycle/molecular-clip complex system can be considered not only as a quadruple-use molecular switch, but can also be operated by three of these stimuli as a three-input molecular NOR-functioning logic gate that may be monitored by UV-visible spectroscopy.

Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests

“…Studying the glycoluril-based molecular clip 15 presenting also TTF sidewalls [ 56 – 57 ], Chiu et al have observed the mixed-valence and radical cation dimer states at high concentration (10 −3 M) and at room temperature [ 58 ]. Indeed, the CV of molecular clip 15 exhibited four consecutive oxidation waves, which were interpreted by a succession of oxidation processes of the TTF sidewalls ( Fig.…”

Tetrathiafulvalene- (TTF-) Derived Oligopyrrolic Macrocycles

“…TTF has proved to be a near-ideal molecular component in such systems. It has been exploited in the design of many different supramolecular architectures, including molecular machines, − molecular flasks, , molecular tweezers, − and molecular switches. − …”

Foldamer‐Tuned Switching Kinetics and Metastability of [2]Rotaxanes

“…It has been established that the donor-acceptor interactions between TTF and bipyridinium units become weakened in less polar solvents owing to the decreased strength of the pstacking interaction. [14] The decomplexation of 1 a and 1 b was substantially slower in less polar solvents than in polar solvents, suggesting that the increase of the free energy of the CT state from a polar solvent to a less polar solvent was considerably smaller than the increase of the free energy of activation for the extrusion of the CBPQT 4+ ring over the foldamer segment caused by the enhancement of their intramolecular hydrogen bonds in less polar solvent.…”