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• W3031296517 endingPage "11846" @default.
• W3031296517 startingPage "11835" @default.
• W3031296517 abstract "We report how the nanoconfined environment, introduced by the mechanical bonds within an electrochemically switchable bistable [2]rotaxane, controls the rotation of a fluorescent molecular rotor, namely, an 8-phenyl-substituted boron dipyrromethene (BODIPY). The electrochemical switching of the bistable [2]rotaxane induces changes in the ground-state coconformation and in the corresponding excited-state properties of the BODIPY rotor. In the starting redox state, when no external potential is applied, the cyclobis(paraquat-p-phenylene) (CBPQT4+) ring component encircles the tetrathiafulvalene (TTF) unit on the dumbbell component, leaving the BODIPY rotor unhindered and exhibiting low fluorescence. Upon oxidation of the TTF unit to a TTF2+ dication, the CBPQT4+ ring is forced toward the molecular rotor, leading to an increased energy barrier for the excited state to rotate the rotor into the state with a high nonradiative rate constant, resulting in an overall 3.4-fold fluorescence enhancement. On the other hand, when the solvent polarity is high enough to stabilize the excited charge-transfer state between the BODIPY rotor and the CBPQT4+ ring, movement of the ring toward the BODIPY rotor produces an unexpectedly strong fluorescence signal decrease as the result of photoinduced electron transfer from the BODIPY rotor to the CBPQT4+ ring. The nanoconfinement effect introduced by mechanical bonding can effectively lead to modulation of the physicochemical properties as observed in this bistable [2]rotaxane. On account of the straightforward synthetic strategy and the facile modulation of switchable electrochromic behavior, our approach could pave the way for the development of new stimuli-responsive materials based on mechanically interlocked molecules for future electro-optical applications, such as sensors, molecular memories, and molecular logic gates." @default.
• W3031296517 created "2020-06-05" @default.
• W3031296517 creator A5016795106 @default.
• W3031296517 creator A5021015026 @default.
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• W3031296517 creator A5035627473 @default.
• W3031296517 creator A5063615214 @default.
• W3031296517 creator A5072522213 @default.
• W3031296517 date "2020-05-29" @default.
• W3031296517 modified "2023-10-12" @default.
• W3031296517 title "Electrochemical Switching of a Fluorescent Molecular Rotor Embedded within a Bistable Rotaxane" @default.
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• W3031296517 doi "https://doi.org/10.1021/jacs.0c03701" @default.
• W3031296517 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/8007092" @default.

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