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Electrochemical Switching of a Fluorescent Molecular Rotor Embedded within a Bistable Rotaxane

Wu, Yilei and Frasconi, Marco and Liu, Wei-Guang and Young, Ryan M. and Goddard, William A., III and Wasielewski, Michael R. and Stoddart, J. Fraser (2020) Electrochemical Switching of a Fluorescent Molecular Rotor Embedded within a Bistable Rotaxane. Journal of the American Chemical Society, 142 (27). pp. 11835-11846. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20200601-140456146

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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 co-conformation 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 the high non-radiative rate constant, resulting in an overall 3.4-fold fluorescent 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, the movement of the ring towards the BODIPY rotor produces an unexpectedly strong fluorescent signal decrease as the result of the photoinduced electron transfer from the BODIPY rotor to the CBPQT⁴⁺ ring. The nanoconfinement effect introduced by mechanical bonding can effectively lead to the 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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.0c03701DOIArticle
https://pubs.acs.org/doi/10.1021/jacs.0c03701PublisherArticle
https://pubs.acs.org/doi/suppl/10.1021/jacs.0c03701/suppl_file/ja0c03701_si_001.pdfPublisherSupporting Information
ORCID:
AuthorORCID
Wu, Yilei0000-0001-6756-1855
Frasconi, Marco0000-0003-2010-175X
Liu, Wei-Guang0000-0002-6633-7795
Goddard, William A., III0000-0003-0097-5716
Wasielewski, Michael R.0000-0003-2920-5440
Stoddart, J. Fraser0000-0003-3161-3697
Additional Information:© 2020 American Chemical Society. Publication Date: May 29, 2020. The authors would like to thank NU for their continued support of this research. The synthesis was supported by the National Science Foundation under CHE-1308107 (J.F.S.). This project was also supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-FG02-99ER14999 (M.R.W.). W.-G.L. and W.A.G. were supported by NSF (CBET). Y.W. thanks the Fulbright Scholar Program for a Fellowship and the NU International Institute of Nanotechnology for a Ryan Fellowship. We thank the personnel in the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University (NU) for their assistance in the collection of the analytical data.
Funders:
Funding AgencyGrant Number
NSFCHE-1308107
Department of Energy (DOE)DE-FG02-99ER14999
Fulbright FoundationUNSPECIFIED
Northwestern UniversityUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1380
Issue or Number:27
Record Number:CaltechAUTHORS:20200601-140456146
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200601-140456146
Official Citation:Electrochemical Switching of a Fluorescent Molecular Rotor Embedded within a Bistable Rotaxane. Yilei Wu, Marco Frasconi, Wei-Guang Liu, Ryan M. Young, William A. Goddard, Michael R. Wasielewski, and J. Fraser Stoddart. Journal of the American Chemical Society. Just Accepted Manuscript; DOI: 10.1021/jacs.0c03701
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:103603
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:01 Jun 2020 21:19
Last Modified:11 Jul 2020 10:06

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