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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. https://resolver.caltech.edu/CaltechAUTHORS:20181212-100140314

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[img] Crystallographic Info File (CIF) (X-ray crystallographic data for (−)-2NDI-1PDI-Δ in CHCl3) - Supplemental Material
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Abstract

The 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
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.8b11201DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/jacs.8b11201PublisherSupporting Information
ORCID:
AuthorORCID
Nalluri, Siva Krishna Mohan0000-0001-6955-3285
Zhou, Jiawang0000-0002-2399-0030
Cheng, Tao0000-0003-4830-177X
Liu, Zhichang0000-0003-3412-512X
Nguyen, Minh T.0000-0002-9043-9580
Patel, Hasmukh A.0000-0002-4968-6686
Krzyaniak, Matthew D.0000-0002-8761-7323
Goddard, William A., III0000-0003-0097-5716
Wasielewski, Michael R.0000-0003-2920-5440
Stoddart, J. Fraser0000-0003-3161-3697
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.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG02-99ER14999
NSFACI-1053575
King Abdulaziz City for Science and Technology (KACST)UNSPECIFIED
Northwestern UniversityUNSPECIFIED
Tianjin UniversityUNSPECIFIED
University of New South WalesUNSPECIFIED
NSFEFRI-ODISSEI-1332411
NSFCBET-1512759
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1311
Issue or Number:3
Record Number:CaltechAUTHORS:20181212-100140314
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20181212-100140314
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
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:91706
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:12 Dec 2018 18:09
Last Modified:26 Oct 2019 02:11

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