Abstract
Molecules that can exist in multiple states with the possibility of toggling between those states based on different stimuli have potential for use in molecular switching or sensing applications. Multimodal chemical or photochemical oxidative switching of an antioxidant-substituted resorcinarene macrocycle is reported. Intramolecular charge-transfer states, involving hemiquinhydrones are probed and these interactions are used to construct an oxidation-state-coupled molecular switching manifold that reports its switch-state conformation via striking variation in its electronic absorption spectra. The coupling of two different oxidation states with two different charge-transfer states within one macrocyclic scaffold delivers up to five different optical outputs. This molecular switching manifold exploits intramolecular coupling of multiple redox active substituents within a single molecule.
Highlights
Molecules that can exist in multiple states with the possibility of toggling between those states based on different stimuli have potential for use in molecular switching or sensing applications
CT interactions occur when electron density is transferred from electron-rich to electron-deficient moieties. When these moieties are respectively hydroquinone and benzoquinone, the resulting C-T complex is known as a quinhydrone[6,7] (Fig. 1a), which is characterized by an intense visible electronic absorption band
The effect of meso-substituent identity on the chemical properties of resorcinarene macrocycles has not been investigated in depth despite the possibility of assessing intramolecular processes based on the isomeric structures of the compounds
Summary
Molecules that can exist in multiple states with the possibility of toggling between those states based on different stimuli have potential for use in molecular switching or sensing applications. The coupling of two different oxidation states with two different charge-transfer states within one macrocyclic scaffold delivers up to five different optical outputs This molecular switching manifold exploits intramolecular coupling of multiple redox active substituents within a single molecule. Numerous classes of molecules, including rotaxanes[2], diarylethenes[3] and luminophores[4], have been studied because of their mechanical, electronic or optical properties In some of these cases, oxidation states or charge-transfer (C-T) interactions play roles in their operation by stabilizing individual switching states with characteristic optical or electronic states[5]. In this study we investigate the coupling of an individual molecule’s oxidation states with their complementary C-T states This combination has not been reported in the context of molecular switching despite possibly providing a greater multiplicity of switchable states in a compact molecule. DtBHP groups have the dual purposes of introducing oxidation state variability while leading to the presence of the requisite phenol and hemiquinone substituents required to establish a hemiquinhydrone C-T complex
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