Discrete Dimers of Redox-Active and Fluorescent Perylene Diimide-Based Rigid Isosceles Triangles in the Solid State
Nalluri, Siva Krishna Mohan and Zhou, Jiawang and Cheng, Tao and Liu, Zhichang and Nguyen, Minh T. and Chen, Tianyang and Patel, Hasmukh A. and Krzyaniak, Matthew D. and Goddard, William A., III and Wasielewski, Michael R. and Stoddart, J. Fraser
(2019)
Discrete Dimers of Redox-Active and Fluorescent Perylene Diimide-Based Rigid Isosceles Triangles in the Solid State.
Journal of the American Chemical Society, 141
(3).
pp. 1290-1303.
ISSN 0002-7863.
doi:10.1021/jacs.8b11201.
https://resolver.caltech.edu/CaltechAUTHORS:20181212-100140314
Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20181212-100140314 AbstractThe development of rigid covalent chiroptical organic materials, with multiple, readily available redox states, which exhibit high photoluminescence, is of particular importance in relation to both organic electronics and photonics. The chemically stable, thermally robust, and redox-active perylene diimide (PDI) fluorophores have received ever-increasing attention owing to their excellent fluorescence quantum yields in solution. Planar PDI derivatives, however, generally suffer from aggregation-caused emission quenching in the solid state. Herein, we report on the design and synthesis of two chiral isosceles triangles, wherein one PDI fluorophore and two pyromellitic diimide (PMDI) or naphthalene diimide (NDI) units are arranged in a rigid cyclic triangular geometry. The optical, electronic, and magnetic properties of the rigid isosceles triangles are fully characterized by a combination of optical spectroscopies, X-ray diffraction (XRD), cyclic voltammetry, and computational modeling techniques. Single-crystal XRD analysis shows that both isosceles triangles form discrete, nearly cofacial PDI–PDI π-dimers in the solid state. While the triangles exhibit fluorescence quantum yields of almost unity in solution, the dimers in the solid state exhibit very weak—yet at least an order of magnitude higher—excimer fluorescence yield in comparison with the almost completely quenched fluorescence of a reference PDI. The triangle containing both NDI and PDI subunits shows superior intramolecular energy transfer from the lowest excited singlet state of the NDI to that of the PDI subunit. Cyclic voltammetry suggests that both isosceles triangles exhibit multiple, easily accessible, and reversible redox states. Applications beckon in arenas related to molecular optoelectronic devices. Item Type: | Article |
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ORCID: | Author | ORCID |
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Nalluri, Siva Krishna Mohan | 0000-0001-6955-3285 | Zhou, Jiawang | 0000-0002-2399-0030 | Cheng, Tao | 0000-0003-4830-177X | Liu, Zhichang | 0000-0003-3412-512X | Nguyen, Minh T. | 0000-0002-9043-9580 | Patel, Hasmukh A. | 0000-0002-4968-6686 | Krzyaniak, Matthew D. | 0000-0002-8761-7323 | Goddard, William A., III | 0000-0003-0097-5716 | Wasielewski, Michael R. | 0000-0003-2920-5440 | Stoddart, J. Fraser | 0000-0003-3161-3697 |
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Additional Information: | © 2018 American Chemical Society.
Received: October 17, 2018; Published: December 11, 2018.
We would like to thank Yilei Wu for assistance with spectroscopy experiments, Charlotte L. Stern for performing single-crystal XRD studies, and Sumit Kewalramani for performing thin-film XRD. This research is a part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). The authors would like to thank KACST, NU, Tianjin University, and the University of New South Wales for their continued support of this research. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE-FG02-99ER14999 (M.R.W.). The quantum mechanics calculations used the resources of the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant no. ACI-1053575. T.C. and W.A.G. were supported by NSF (EFRI-ODISSEI-1332411) and NSF (CBET 1512759).
The authors declare no competing financial interest. |
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Funders: | Funding Agency | Grant Number |
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Department of Energy (DOE) | DE-FG02-99ER14999 | NSF | ACI-1053575 | King Abdulaziz City for Science and Technology (KACST) | UNSPECIFIED | Northwestern University | UNSPECIFIED | Tianjin University | UNSPECIFIED | University of New South Wales | UNSPECIFIED | NSF | EFRI-ODISSEI-1332411 | NSF | CBET-1512759 |
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Other Numbering System: | Other Numbering System Name | Other Numbering System ID |
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WAG | 1360 |
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Issue or Number: | 3 |
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DOI: | 10.1021/jacs.8b11201 |
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Record Number: | CaltechAUTHORS:20181212-100140314 |
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Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20181212-100140314 |
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Official Citation: | Discrete Dimers of Redox-Active and Fluorescent Perylene Diimide-Based Rigid Isosceles Triangles in the Solid State.
Siva Krishna Mohan Nalluri, Jiawang Zhou, Tao Cheng, Zhichang Liu, Minh T. Nguyen, Tianyang Chen, Hasmukh A. Patel, Matthew D. Krzyaniak, William A. Goddard III, Michael R. Wasielewski, and J. Fraser Stoddart.
Journal of the American Chemical Society 2019 141 (3), 1290-1303.
DOI: 10.1021/jacs.8b11201 |
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Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. |
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ID Code: | 91706 |
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Collection: | CaltechAUTHORS |
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Deposited By: |
Tony Diaz
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Deposited On: | 12 Dec 2018 18:09 |
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Last Modified: | 16 Nov 2021 03:43 |
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