Discrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State
Abstract
In the solid state the properties of organic radicals depend heavily on radical-radical interactions that are influenced by the superstructure of the crystalline phase. Here, we report the synthesis and characterization of a substituted tetracationic cyclophane, cyclobis(paraquat-p-1,4- dimethoxyphenylene), and outline how its bisradical dicationic redox state associates with the methyl viologen radical cation (MV•+) to give a trisradical tricationic inclusion complex. The (super)structures of the reduced cyclophane and this 1:1 complex in the solid-state deviate from the analogous (super)structures observed for the reduced state of cyclobis(paraquat-p-phenylene) and that of its trisradical tricationic complex. Titration experiments with a range of guests reveal that the methoxy substituents on the para-xylenyl do not influence significantly of the binding affinity of the cyclophane for small neutral guests, whereas the affinity decreases by an order of magnitude for larger radical cationic guests such as MV•+. X-Ray diffraction reveals that the solid- state structures of the tricationic trisradical complexes to be a discrete entity with weak intermolecular orbital overlap between the neighboring complexes. Transient nutation EPR experiment and DFT calculations confirm that the complex has a doublet spin configuration in the ground state as a result of the strong orbital overlap within the complex, while themore »
- Authors:
-
[1];
[1];
[2];
[1];
[1];
[1];
[1];
[1];
[1];
[1];
[1];
[3]
- Northwestern Univ., Evanston, IL (United States)
- Northwestern Univ., Evanston, IL (United States); Univ. of Reading (United Kingdom)
- Northwestern Univ., Evanston, IL (United States); Univ. of New South Wales, Sydney, NSW (Australia)
- Publication Date:
- Research Org.:
- Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1798263
- Grant/Contract Number:
- SC0004752
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 143; Journal Issue: 1; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Crystals; Superstructures; Counterions; Electron paramagnetic resonance spectroscopy; Quantum mechanics
Citation Formats
Anamimoghadam, Ommid, Jones, Leighton O., Cooper, James A., Beldjoudi, Yassine, Nguyen, Minh T., Liu, Wenqi, Krzyaniak, Matthew D., Pezzato, Cristian, Stern, Charlotte L., Patel, Hasmukh A., Wasielewski, Michael R., Schatz, George C., and Stoddart, J. Fraser. Discrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State. United States: N. p., 2020.
Web. doi:10.1021/jacs.0c07148.
Anamimoghadam, Ommid, Jones, Leighton O., Cooper, James A., Beldjoudi, Yassine, Nguyen, Minh T., Liu, Wenqi, Krzyaniak, Matthew D., Pezzato, Cristian, Stern, Charlotte L., Patel, Hasmukh A., Wasielewski, Michael R., Schatz, George C., & Stoddart, J. Fraser. Discrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State. United States. https://doi.org/10.1021/jacs.0c07148
Anamimoghadam, Ommid, Jones, Leighton O., Cooper, James A., Beldjoudi, Yassine, Nguyen, Minh T., Liu, Wenqi, Krzyaniak, Matthew D., Pezzato, Cristian, Stern, Charlotte L., Patel, Hasmukh A., Wasielewski, Michael R., Schatz, George C., and Stoddart, J. Fraser. Mon .
"Discrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State". United States. https://doi.org/10.1021/jacs.0c07148. https://www.osti.gov/servlets/purl/1798263.
@article{osti_1798263,
title = {Discrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State},
author = {Anamimoghadam, Ommid and Jones, Leighton O. and Cooper, James A. and Beldjoudi, Yassine and Nguyen, Minh T. and Liu, Wenqi and Krzyaniak, Matthew D. and Pezzato, Cristian and Stern, Charlotte L. and Patel, Hasmukh A. and Wasielewski, Michael R. and Schatz, George C. and Stoddart, J. Fraser},
abstractNote = {In the solid state the properties of organic radicals depend heavily on radical-radical interactions that are influenced by the superstructure of the crystalline phase. Here, we report the synthesis and characterization of a substituted tetracationic cyclophane, cyclobis(paraquat-p-1,4- dimethoxyphenylene), and outline how its bisradical dicationic redox state associates with the methyl viologen radical cation (MV•+) to give a trisradical tricationic inclusion complex. The (super)structures of the reduced cyclophane and this 1:1 complex in the solid-state deviate from the analogous (super)structures observed for the reduced state of cyclobis(paraquat-p-phenylene) and that of its trisradical tricationic complex. Titration experiments with a range of guests reveal that the methoxy substituents on the para-xylenyl do not influence significantly of the binding affinity of the cyclophane for small neutral guests, whereas the affinity decreases by an order of magnitude for larger radical cationic guests such as MV•+. X-Ray diffraction reveals that the solid- state structures of the tricationic trisradical complexes to be a discrete entity with weak intermolecular orbital overlap between the neighboring complexes. Transient nutation EPR experiment and DFT calculations confirm that the complex has a doublet spin configuration in the ground state as a result of the strong orbital overlap within the complex, while the quartet-state spin configuration is higher in energy and so is inaccessible at ambient temperature. The superconducting quantum interference device (SQUID) measurement reveals that trisradical tricationic complexes interact antiferromagnetically (J/k = - 2.33 K) and form a 1D Heisenberg antiferromagnetic chain along the a-axis in the crystal. Furthermore, these results offer new insights into the design and synthesis of organic magnetic materials based on host-guest inclusion complexes.},
doi = {10.1021/jacs.0c07148},
journal = {Journal of the American Chemical Society},
number = 1,
volume = 143,
place = {United States},
year = {Mon Dec 21 00:00:00 EST 2020},
month = {Mon Dec 21 00:00:00 EST 2020}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Design of organic metals and superconductors
journal, July 1975
- Haddon, Robert C.
- Nature, Vol. 256, Issue 5516
Conducting charge-transfer salts based on neutral π-radicals
journal, October 1993
- Bryan, C. D.; Cordes, A. W.; Fleming, R. M.
- Nature, Vol. 365, Issue 6449
The Power of Packing: Metallization of an Organic Semiconductor
journal, January 2017
- Mailman, Aaron; Leitch, Alicea A.; Yong, Wenjun
- Journal of the American Chemical Society, Vol. 139, Issue 6
Organic Diradicals and Polyradicals: From Spin Coupling to Magnetism?
journal, June 1994
- Rajca, Andrzej
- Chemical Reviews, Vol. 94, Issue 4
Recent Advances in Organic Radicals and Their Magnetism
journal, November 2016
- Kumar, Sharvan; Kumar, Yogendra; Keshri, Sudhir
- Magnetochemistry, Vol. 2, Issue 4
High stability and luminescence efficiency in donor–acceptor neutral radicals not following the Aufbau principle
journal, July 2019
- Guo, Haoqing; Peng, Qiming; Chen, Xian-Kai
- Nature Materials, Vol. 18, Issue 9
Understanding the luminescent nature of organic radicals for efficient doublet emitters and pure-red light-emitting diodes
journal, June 2020
- Abdurahman, Alim; Hele, Timothy J. H.; Gu, Qinying
- Nature Materials, Vol. 19, Issue 11
Multifunctional Dithiadiazolyl Radicals: Fluorescence, Electroluminescence, and Photoconducting Behavior in Pyren-1′-yl-dithiadiazolyl
journal, April 2018
- Beldjoudi, Yassine; Nascimento, Mitchell A.; Cho, Yong Joo
- Journal of the American Chemical Society, Vol. 140, Issue 20
A fluorescent dithiadiazolyl radical: structure and optical properties of phenanthrenyl dithiadiazolyl in solution and polymer composites
journal, January 2017
- Beldjoudi, Yassine; Osorio-Román, Igor; Nascimento, Mitchell A.
- Journal of Materials Chemistry C, Vol. 5, Issue 11
High-Power-Density Organic Radical Batteries
journal, February 2017
- Friebe, Christian; Schubert, Ulrich S.
- Topics in Current Chemistry, Vol. 375, Issue 1
Synthesis, Physical Properties, and Reactivity of Stable, π-Conjugated, Carbon-Centered Radicals
journal, February 2019
- Kubo, Takashi
- Molecules, Vol. 24, Issue 4
Aromaticity on the Pancake-Bonded Dimer of Neutral Phenalenyl Radical as Studied by MS and NMR Spectroscopies and NICS Analysis
journal, March 2006
- Suzuki, Shuichi; Morita, Yasushi; Fukui, Kozo
- Journal of the American Chemical Society, Vol. 128, Issue 8
Evidence of σ- and π-Dimerization in a Series of Phenalenyls
journal, December 2014
- Mou, Zhongyu; Uchida, Kazuyuki; Kubo, Takashi
- Journal of the American Chemical Society, Vol. 136, Issue 52
Mixed valence salts based on carbon-centered neutral radical crystals
journal, August 2018
- Murata, Tsuyoshi; Yamada, Chiaki; Furukawa, Ko
- Communications Chemistry, Vol. 1, Issue 1
Influence of organic cations on the stacking of semiquinone radical anions
journal, January 2019
- Molčanov, Krešimir; Milašinović, Valentina; Ivić, Nives
- CrystEngComm, Vol. 21, Issue 45
A Concise Synthetic Strategy for Accessing Ambient Stable Bisphenalenyls toward Achieving Electroactive Open-Shell π-Conjugated Materials
journal, January 2019
- Wehrmann, Caleb M.; Charlton, Ryan T.; Chen, Mark S.
- Journal of the American Chemical Society, Vol. 141, Issue 7
MnII(TCNE)3/2(I3)1/2-A 3D Network-Structured Organic-Based Magnet and Comparison to a 2D Analog
journal, May 2010
- Stone, Kevin H.; Stephens, Peter W.; McConnell, Amber C.
- Advanced Materials, Vol. 22, Issue 23
Crystal engineering with dithiadiazolyl radicals
journal, January 2011
- Haynes, Delia A.
- CrystEngComm, Vol. 13, Issue 15
The First Electronically Stabilized Phenalenyl Radical: Effect of Substituents on Solution Chemistry and Solid-State Structure
journal, March 2007
- Beer, Leanne; Mandal, Swadhin K.; Reed, Robert W.
- Crystal Growth & Design, Vol. 7, Issue 4
A Stable Neutral Hydrocarbon Radical: Synthesis, Crystal Structure, and Physical Properties of 2,5,8-Tri- tert -butyl-phenalenyl
journal, February 1999
- Goto, Kosaburo; Kubo, Takashi; Yamamoto, Kagetoshi
- Journal of the American Chemical Society, Vol. 121, Issue 7
Room-Temperature Magnetic Bistability in Organic Radical Crystals
journal, October 1999
- Fujita, W.
- Science, Vol. 286, Issue 5438
Synthesis, crystal structures, electronic structure and magnetic behaviour of the trithiatriazapentalenyl radical, C2S3N3
journal, January 2001
- McManus, Gordon D.; Rawson, Jeremy M.; Feeder, Neil
- Journal of Materials Chemistry, Vol. 11, Issue 8
Spontaneous Magnetization in a Sulfur–Nitrogen Radical at 36 K
journal, November 1996
- Banister, Arthur J.; Bricklebank, Neil; Lavender, Ian
- Angewandte Chemie International Edition in English, Vol. 35, Issue 21
Pressure-Induced Enhancement of Magnetic-Ordering Temperature in an Organic Radical to 70 K: A Magnetostructural Correlation
journal, June 2012
- Thomson, Richard I.; Pask, Christopher M.; Lloyd, Gareth O.
- Chemistry - A European Journal, Vol. 18, Issue 28
A Thiazyl-Based Organic Ferromagnet
journal, October 2003
- Alberola, Antonio; Less, Robert J.; Pask, Christopher M.
- Angewandte Chemie International Edition, Vol. 42, Issue 39
A Benzene-1,3,5-Triaminyl Radical Fused with Zn II -Porphyrins: Remarkable Stability and a High-Spin Quartet Ground State
journal, March 2018
- Shimizu, Daiki; Osuka, Atsuhiro
- Angewandte Chemie International Edition, Vol. 57, Issue 14
Tuning the stability of organic radicals: from covalent approaches to non-covalent approaches
journal, January 2020
- Tang, Bohan; Zhao, Jiantao; Xu, Jiang-Fei
- Chemical Science, Vol. 11, Issue 5
Stable π-electron systems and new aromatic structures
journal, January 1958
- Reid, D. H.
- Tetrahedron, Vol. 3, Issue 3
Electrical conductivity by the bis(1,3-dithiole)-bis(1,3-dithiolium) system
journal, January 1972
- Wudl, Fred; Wobschall, Darold; Hufnagel, Earl J.
- Journal of the American Chemical Society, Vol. 94, Issue 2
Optical properties of the radical cation tetrathiafulvalenium (TT ) in its mixed-valence and monovalence halide salts
journal, January 1979
- Torrance, J. B.; Scott, B. A.; Welber, B.
- Physical Review B, Vol. 19, Issue 2
Stable Free Radicals. II. The Reduction of 1-Methyl-4-cyanopyridinium Ion to Methylviologen Cation Radical
journal, December 1964
- Kosower, Edward M.; Cotter, John L.
- Journal of the American Chemical Society, Vol. 86, Issue 24
Isolation and oxidation-reduction of methylviologen cation radicals. Novel disproportionation in charge-transfer salts by x-ray crystallography
journal, June 1990
- Bockman, T. M.; Kochi, J. K.
- The Journal of Organic Chemistry, Vol. 55, Issue 13, p. 4127-4135
The Viologen Cation Radical Pimer: A Case of Dispersion-Driven Bonding
journal, July 2017
- Geraskina, Margarita R.; Dutton, Andrew S.; Juetten, Mark J.
- Angewandte Chemie International Edition, Vol. 56, Issue 32
Molecular recognition and switching via radical dimerization
journal, September 2010
- Spruell, Jason M.
- Pure and Applied Chemistry, Vol. 82, Issue 12
Pancake Bonding: An Unusual Pi-Stacking Interaction
journal, November 2018
- Kertesz, Miklos
- Chemistry - A European Journal, Vol. 25, Issue 2
The chemistry of the phenalenes
journal, January 1965
- Reid, D. H.
- Quarterly Reviews, Chemical Society, Vol. 19, Issue 3
Cyclobis(paraquat-p-phenylene): a novel synthetic receptor for amino acids with electron-rich aromatic moieties
journal, May 1991
- Goodnow, Timothy T.; Reddington, Mark V.; Stoddart, J. Fraser
- Journal of the American Chemical Society, Vol. 113, Issue 11
Cyclophanes with self-recognising components
journal, January 1995
- Anelli, Pier-Lucio; Asakawa, Masumi; Ashton, Peter R.
- Journal of the Chemical Society, Chemical Communications, Issue 24
Redox Control of the Binding Modes of an Organic Receptor
journal, August 2015
- Frasconi, Marco; Fernando, Isurika R.; Wu, Yilei
- Journal of the American Chemical Society, Vol. 137, Issue 34
A Boat-Shaped Tetracationic Macrocycle with a Semiconducting Organic Framework
journal, April 2017
- Nguyen, Minh T.; Krzyaniak, Matthew D.; Owczarek, Magdalena
- Angewandte Chemie International Edition, Vol. 56, Issue 21
Viologen-inspired functional materials: synthetic strategies and applications
journal, January 2019
- Ding, Junjie; Zheng, Caini; Wang, Luxin
- Journal of Materials Chemistry A, Vol. 7, Issue 41
A polyrotaxanated covalent organic network based on viologen and cucurbit[7]uril
journal, September 2019
- Das, Gobinda; Sharma, Sudhir Kumar; Prakasam, Thirumurugan
- Communications Chemistry, Vol. 2, Issue 1
Cyclobis(paraquat-p-phenylene). A Tetracationic Multipurpose Receptor
journal, November 1988
- Odell, Barbara; Reddington, Mark V.; Slawin, Alexandra M. Z.
- Angewandte Chemie International Edition in English, Vol. 27, Issue 11, p. 1547-1550
The complexation of tetrathiafulvalene by cyclobis(Paraquat-p-phenylene)
journal, January 1991
- Philp, Douglas; Slawin, Alexandra M. Z.; Spencer, Neil
- Journal of the Chemical Society, Chemical Communications, Issue 22
A Semiconducting Organic Radical Cationic Host–Guest Complex
journal, October 2012
- Fahrenbach, Albert C.; Sampath, Srinivasan; Late, Dattatray J.
- ACS Nano, Vol. 6, Issue 11
The self assembly of controllable [2]catenanes
journal, January 1994
- Ashton, Peter R.; Ballardini, Roberto; Balzani, Vincenzo
- J. Chem. Soc., Chem. Commun., Issue 2
A self-organised layered superstructure of arrayed [2]pseudorotaxanes
journal, January 1994
- Ashton, Peter R.; Philp, Douglas; Spencer, Neil
- Journal of the Chemical Society, Chemical Communications, Issue 2
A chemically and electrochemically switchable molecular shuttle
journal, May 1994
- Bissell, Richard A.; Córdova, Emilio; Kaifer, Angel E.
- Nature, Vol. 369, Issue 6476
A Radically Configurable Six-State Compound
journal, January 2013
- Barnes, J. C.; Fahrenbach, A. C.; Cao, D.
- Science, Vol. 339, Issue 6118
Catenanes: Fifty Years of Molecular Links
journal, May 2015
- Gil-Ramírez, Guzmán; Leigh, David A.; Stephens, Alexander J.
- Angewandte Chemie International Edition, Vol. 54, Issue 21
Mechanically Interlocked Molecules (MIMs)-Molecular Shuttles, Switches, and Machines (Nobel Lecture)
journal, August 2017
- Stoddart, J. Fraser
- Angewandte Chemie International Edition, Vol. 56, Issue 37
An artificial molecular pump
journal, May 2015
- Cheng, Chuyang; McGonigal, Paul R.; Schneebeli, Severin T.
- Nature Nanotechnology, Vol. 10, Issue 6
An efficient artificial molecular pump
journal, August 2017
- Pezzato, Cristian; Nguyen, Minh T.; Cheng, Chuyang
- Tetrahedron, Vol. 73, Issue 33
Controlling Dual Molecular Pumps Electrochemically
journal, June 2018
- Pezzato, Cristian; Nguyen, Minh T.; Kim, Dong Jun
- Angewandte Chemie International Edition, Vol. 57, Issue 30
A precise polyrotaxane synthesizer
journal, June 2020
- Qiu, Yunyan; Song, Bo; Pezzato, Cristian
- Science, Vol. 368, Issue 6496
Radically enhanced molecular recognition
journal, December 2009
- Trabolsi, Ali; Khashab, Niveen; Fahrenbach, Albert C.
- Nature Chemistry, Vol. 2, Issue 1
Solution-Phase Mechanistic Study and Solid-State Structure of a Tris(bipyridinium radical cation) Inclusion Complex
journal, February 2012
- Fahrenbach, Albert C.; Barnes, Jonathan C.; Lanfranchi, Don Antoine
- Journal of the American Chemical Society, Vol. 134, Issue 6
Influence of Constitution and Charge on Radical Pairing Interactions in Tris-radical Tricationic Complexes
journal, June 2016
- Cheng, Chuyang; Cheng, Tao; Xiao, Hai
- Journal of the American Chemical Society, Vol. 138, Issue 26
Pairing-up viologen cations and dications: a microscopic investigation of van der Waals interactions
journal, January 2018
- Gourlaouen, Christophe; Vela, Sergi; Choua, Sylvie
- Physical Chemistry Chemical Physics, Vol. 20, Issue 44
Viologen cyclophanes: redox controlled host–guest interactions
journal, January 2015
- Berville, Mathilde; Karmazin, Lydia; Wytko, Jennifer A.
- Chemical Communications, Vol. 51, Issue 87
Flexible Viologen Cyclophanes: Odd/Even Effects on Intramolecular Interactions
journal, February 2017
- Berville, Mathilde; Choua, Sylvie; Gourlaouen, Christophe
- ChemPhysChem, Vol. 18, Issue 7
Quadruple stacking of macrocyclic viologen radical-cations
journal, September 2017
- Murray, Claire A.; Zhu, Zhixue; Cardin, Christine J.
- Supramolecular Chemistry, Vol. 30, Issue 9
Synthesis of Ex n Box Cyclophanes
journal, November 2013
- Barnes, Jonathan C.; Juríček, Michal; Vermeulen, Nicolaas A.
- The Journal of Organic Chemistry, Vol. 78, Issue 23
Self-complementary Tetracationic Cyclophanes Containing 4,4′-Bipyridinium and 2,5-Dimethoxy-1,4-xylyl Subunits
journal, April 2005
- Srinivasan, Kannupal; Rajakumar, Perumal
- Supramolecular Chemistry, Vol. 17, Issue 3
Cyclotris(paraquat- p -phenylenes)
journal, August 2019
- Anamimoghadam, Ommid; Cooper, James A.; Nguyen, Minh T.
- Angewandte Chemie International Edition, Vol. 58, Issue 39
A Three-Pole Supramolecular Switch †
journal, April 1999
- Ashton, Peter R.; Balzani, Vincenzo; Becher, Jan
- Journal of the American Chemical Society, Vol. 121, Issue 16
Binding Studies between Tetrathiafulvalene Derivatives and Cyclobis(paraquat- p -phenylene)
journal, May 2001
- Nielsen, Mogens Brøndsted; Jeppesen, Jan Oskar; Lau, Jesper
- The Journal of Organic Chemistry, Vol. 66, Issue 10
Charge recombination in cyclophane-derived, intimate radical ion pairs
journal, June 1993
- Benniston, Andrew C.; Harriman, Anthony; Philp, Douglas
- Journal of the American Chemical Society, Vol. 115, Issue 12
Determining association constants from titration experiments in supramolecular chemistry
journal, January 2011
- Thordarson, Pall
- Chem. Soc. Rev., Vol. 40, Issue 3
High-Efficiency Gold Recovery Using Cucurbit[6]uril
journal, July 2020
- Wu, Huang; Jones, Leighton O.; Wang, Yu
- ACS Applied Materials & Interfaces, Vol. 12, Issue 34
Structural, Magnetic, and Optical Studies of the Polymorphic 9′-Anthracenyl Dithiadiazolyl Radical
journal, March 2019
- Beldjoudi, Yassine; Arauzo, Ana; Campo, Javier
- Journal of the American Chemical Society, Vol. 141, Issue 17