Anion-Mediated Photophysical Behavior in a C60 Fullerene [3]Rotaxane Shuttle

• DOI: 10.1021/jacs.7b12819
• Publication Date: 2018-01-16T19:39:30Z
• Authors: Timothy A. Barendt; Ilija Rašović; Maria A. Lebedeva; George A. Farrow; Alexander Auty; Dimitri Chekulaev; Igor V. Sazanovich; Julia A. Weinstein; Kyriakos Porfyrakis; Paul D. Beer
• Keywords: Rotaxane

By addressing the challenge of controlling molecular motion, mechanically interlocked machines are primed for a variety applications in field nanotechnology. Specifically, designed manipulation communication pathways between electron donor and acceptor moieties that strategically integrated into dynamic photoactive rotaxanes catenanes may lead to efficient artificial photosynthetic devices. In this pursuit, novel [3]rotaxane shuttle consisting four-station bis-naphthalene diimide (NDI) central C60 fullerene bis-triazolium axle component two bonded ferrocenyl-functionalized isophthalamide anion binding site-containing macrocycles is constructed using an template synthetic methodology. Dynamic coconformational recognition-mediated shuttling, which alters relative positions motifs [3]rotaxane's macrocycle components, demonstrated initially by 1H NMR spectroscopy. Detailed steady-state time-resolved UV–vis–IR absorption emission spectroscopies as well electrochemical studies employed further probe anion-dependent positional macrocycle–axle station state shuttle, revealing striking on/off switchable response induced binding. chloride coconformation, where reside at center component, precludes transfer NDI, resulting switching-on from NDI fluorophore concomitant formation fullerene-based charge-separated state. stark contrast, absence hexafluorophosphate salt, peripheral stations, quenching via NDI-containing Such anion-mediated control photophysical behavior rotaxane through motion unprecedented.