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Title: Rotaxane rings promote oblique packing and extended lifetimes in DNA-templated molecular dye aggregates

Abstract

Abstract Molecular excitons play a central role in natural and artificial light harvesting, organic electronics, and nanoscale computing. The structure and dynamics of molecular excitons, critical to each application, are sensitively governed by molecular packing. Deoxyribonucleic acid (DNA) templating is a powerful approach that enables controlled aggregation via sub-nanometer positioning of molecular dyes. However, finer sub-Angstrom control of dye packing is needed to tailor excitonic properties for specific applications. Here, we show that adding rotaxane rings to squaraine dyes templated with DNA promotes an elusive oblique packing arrangement with highly desirable optical properties. Specifically, dimers of these squaraine:rotaxanes exhibit an absorption spectrum with near-equal intensity excitonically split absorption bands. Theoretical analysis indicates that the transitions are mostly electronic in nature and only have similar intensities over a narrow range of packing angles. Compared with squaraine dimers, squaraine:rotaxane dimers also exhibit extended excited-state lifetimes and less structural heterogeneity. The approach proposed here may be generally useful for optimizing excitonic materials for a variety of applications ranging from solar energy conversion to quantum information science.

Authors:
; ORCiD logo; ; ; ORCiD logo; ; ORCiD logo; ; ; ORCiD logo; ; ; ORCiD logo
Publication Date:
Research Org.:
Boise State Univ., ID (United States)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
OSTI Identifier:
1766582
Alternate Identifier(s):
OSTI ID: 1760019
Grant/Contract Number:  
SC0020089
Resource Type:
Published Article
Journal Name:
Communications Chemistry
Additional Journal Information:
Journal Name: Communications Chemistry Journal Volume: 4 Journal Issue: 1; Journal ID: ISSN 2399-3669
Publisher:
Nature Publishing Group
Country of Publication:
United Kingdom
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Barclay, Matthew S., Roy, Simon K., Huff, Jonathan S., Mass, Olga A., Turner, Daniel B., Wilson, Christopher K., Kellis, Donald L., Terpetschnig, Ewald A., Lee, Jeunghoon, Davis, Paul H., Yurke, Bernard, Knowlton, William B., and Pensack, Ryan D.. Rotaxane rings promote oblique packing and extended lifetimes in DNA-templated molecular dye aggregates. United Kingdom: N. p., 2021. Web. https://doi.org/10.1038/s42004-021-00456-8.
Barclay, Matthew S., Roy, Simon K., Huff, Jonathan S., Mass, Olga A., Turner, Daniel B., Wilson, Christopher K., Kellis, Donald L., Terpetschnig, Ewald A., Lee, Jeunghoon, Davis, Paul H., Yurke, Bernard, Knowlton, William B., & Pensack, Ryan D.. Rotaxane rings promote oblique packing and extended lifetimes in DNA-templated molecular dye aggregates. United Kingdom. https://doi.org/10.1038/s42004-021-00456-8
Barclay, Matthew S., Roy, Simon K., Huff, Jonathan S., Mass, Olga A., Turner, Daniel B., Wilson, Christopher K., Kellis, Donald L., Terpetschnig, Ewald A., Lee, Jeunghoon, Davis, Paul H., Yurke, Bernard, Knowlton, William B., and Pensack, Ryan D.. Thu . "Rotaxane rings promote oblique packing and extended lifetimes in DNA-templated molecular dye aggregates". United Kingdom. https://doi.org/10.1038/s42004-021-00456-8.
@article{osti_1766582,
title = {Rotaxane rings promote oblique packing and extended lifetimes in DNA-templated molecular dye aggregates},
author = {Barclay, Matthew S. and Roy, Simon K. and Huff, Jonathan S. and Mass, Olga A. and Turner, Daniel B. and Wilson, Christopher K. and Kellis, Donald L. and Terpetschnig, Ewald A. and Lee, Jeunghoon and Davis, Paul H. and Yurke, Bernard and Knowlton, William B. and Pensack, Ryan D.},
abstractNote = {Abstract Molecular excitons play a central role in natural and artificial light harvesting, organic electronics, and nanoscale computing. The structure and dynamics of molecular excitons, critical to each application, are sensitively governed by molecular packing. Deoxyribonucleic acid (DNA) templating is a powerful approach that enables controlled aggregation via sub-nanometer positioning of molecular dyes. However, finer sub-Angstrom control of dye packing is needed to tailor excitonic properties for specific applications. Here, we show that adding rotaxane rings to squaraine dyes templated with DNA promotes an elusive oblique packing arrangement with highly desirable optical properties. Specifically, dimers of these squaraine:rotaxanes exhibit an absorption spectrum with near-equal intensity excitonically split absorption bands. Theoretical analysis indicates that the transitions are mostly electronic in nature and only have similar intensities over a narrow range of packing angles. Compared with squaraine dimers, squaraine:rotaxane dimers also exhibit extended excited-state lifetimes and less structural heterogeneity. The approach proposed here may be generally useful for optimizing excitonic materials for a variety of applications ranging from solar energy conversion to quantum information science.},
doi = {10.1038/s42004-021-00456-8},
journal = {Communications Chemistry},
number = 1,
volume = 4,
place = {United Kingdom},
year = {2021},
month = {2}
}

Journal Article:
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https://doi.org/10.1038/s42004-021-00456-8

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