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Elucidation of Diverse Solid‐State Packing in a Family of Electron‐Deficient Expanded Helicenes via Microcrystal Electron Diffraction (MicroED)

Samkian, Adrian E. and Kiel, Gavin R. and Jones, Christopher G. and Bergman, Harrison M. and Oktawiec, Julia and Nelson, Hosea M. and Tilley, T. Don (2021) Elucidation of Diverse Solid‐State Packing in a Family of Electron‐Deficient Expanded Helicenes via Microcrystal Electron Diffraction (MicroED). Angewandte Chemie International Edition, 60 (5). pp. 2493-2499. ISSN 1433-7851. doi:10.1002/anie.202012213. https://resolver.caltech.edu/CaltechAUTHORS:20210811-225351099

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Abstract

Solid-state packing plays a defining role in the properties of a molecular organic material, but it is difficult to elucidate in the absence of single crystals that are suitable for X-ray diffraction. Herein, we demonstrate the coupling of divergent synthesis with microcrystal electron diffraction (MicroED) for rapid assessment of solid-state packing motifs, using a class of chiral nanocarbons—expanded helicenes—as a proof of concept. Two highly selective oxidative dearomatizations of a readily accessible helicene provided a divergent route to four electron-deficient analogues containing quinone or quinoxaline units. Crystallization efforts consistently yielded microcrystals that were unsuitable for single-crystal X-ray diffraction, but ideal for MicroED. This technique facilitated the elucidation of solid-state structures of all five compounds with <1.1 Å resolution. The otherwise-inaccessible data revealed a range of notable packing behaviors, including four different space groups, homochirality in a crystal for a helicene with an extremely low enantiomerization barrier, and nanometer scale cavities.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/anie.202012213DOIArticle
https://doi.org/10.26434/chemrxiv.12925511.v2DOIDiscussion Paper
ORCID:
AuthorORCID
Samkian, Adrian E.0000-0002-0068-3572
Kiel, Gavin R.0000-0001-6449-8547
Bergman, Harrison M.0000-0001-6482-2837
Oktawiec, Julia0000-0002-2895-3327
Nelson, Hosea M.0000-0002-4666-2793
Tilley, T. Don0000-0002-6671-9099
Alternate Title:MicroED Elucidation of Diverse Solid-State Packing in a Family of Electron-Deficient Expanded Helicenes
Additional Information:© 2020 Wiley-VCH. Issue Online: 25 January 2021. Version of Record online: 27 November 2020. Accepted manuscript online: 08 October 2020. Manuscript received: 07 September 2020. A large portion of this work was funded by the National Science Foundation under Grant No. CHE-1708210. C.G.J. acknowledges the National Science Foundation Graduate Research Fellowship Program (DGE-1650604), the Christopher S. Foote Fellowship, and the Pat Tillman Foundation for funding. J.O. acknowledges the National Science Foundation Graduate Research Fellowship Program (DGE-1650604) for funding. H.M.N. acknowledges the Packard Foundation and Bristol Myers Squibb for generous funding. A.E.S. thanks Robert H. Grubbs for use of facilities and helpful discussions. The authors thank Jose Rodriguez, Duilio Cascio, Michael R. Sawaya and Michael J. Collazo (UCLA) for assistance with MicroED data collection and processing, and Vincent LaVallo, Yan Xu and William Wolf for helpful general discussions. The computational work was performed at the UC Berkeley Molecular Graphics and Computation Facility (MGCF), which is supported by the National Institute of Health (Grant No. NIH S10OD023532), and the authors thank Dave Small for his assistance with these calculations. This work incorporates data collected at the Northeastern Collaborative Access Team (NE-CAT) beamlines at Argonne National Laboratory. NE-CAT is funded by the NIH-NIGMS (Grant No. P30 GM124165). The Pilatus 6M detector on the 24-ID-C beamline is funded by NIH-ORIP HEI (Grant No. S10 RR029205). This work also used resources at the Advanced Photon Source, a U.S. Department of Energy Office of Science User Facility operated by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The UCLA-DOE Institute's X-ray Crystallography Core Facility is supported by the U.S. Department of Energy (Grant No. DE-FC02-02ER63421). The authors declare no conflict of interest.
Funders:
Funding AgencyGrant Number
NSFCHE-1708210
NSF Graduate Research FellowshipDGE-1650604
UCLAUNSPECIFIED
Pat Tillman FoundationUNSPECIFIED
David and Lucile Packard FoundationUNSPECIFIED
Bristol-Myers SquibbUNSPECIFIED
NIHS10OD023532
NIHP30 GM124165
NIHS10 RR029205
Department of Energy (DOE)DE-AC02-06CH11357
Department of Energy (DOE)DE-FC02-02ER63421
Subject Keywords:chiral nanocarbon; helicenes; microED; polycyclic aromatic hydrocarbon (PAH) self-assembly
Issue or Number:5
DOI:10.1002/anie.202012213
Record Number:CaltechAUTHORS:20210811-225351099
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210811-225351099
Official Citation:A. E. Samkian, G. R. Kiel, C. G. Jones, H. M. Bergman, J. Oktawiec, H. M. Nelson, T. D. Tilley, Angew. Chem. Int. Ed. 2021, 60, 2493.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:110208
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:12 Aug 2021 22:34
Last Modified:13 Aug 2021 17:45

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