Ion Pair Driven Self-Assembly of a Flexible Bis-Zwitterion in Polar Solution: Formation of Discrete Nanometer-Sized Cyclic Dimers
Abstract

The self-complementary flexible bis-zwitterion 1 forms discrete nanometer-sized cyclic dimers via ion pair driven self-assembly even in polar solvents. The existence of such dimers was confirmed by DOSY NMR, FAB-MS, and scattering experiments (DLS, SANS) which all indicate the concentration-dependent formation of cyclic dimers with a hydrodynamic radius of rH ≈ 2.5 nm in solution.
*
In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.
†
University of Würzburg.
‡
Max Planck Institute for Polymer Research.
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- Yuren Sun, Jun Gu, Hongyu Wang, Jonathan L. Sessler, Pall Thordarson, Yue-Jian Lin, Hegui Gong. AAAA–DDDD Quadruple H-Bond-Assisted Ionic Interactions: Robust Bis(guanidinium)/Dicarboxylate Heteroduplexes in Water. Journal of the American Chemical Society 2019, 141
(51)
, 20146-20154. https://doi.org/10.1021/jacs.9b09503
- Seyedali Monemian, Keon-Soo Jang, Hossein Ghassemi, and LaShanda T. J. Korley . Probing the Interplay of Ultraviolet Cross-Linking and Noncovalent Interactions in Supramolecular Elastomers. Macromolecules 2014, 47
(16)
, 5633-5642. https://doi.org/10.1021/ma501183a
- Junyong Jo, András Olasz, Chun-Hsing Chen, and Dongwhan Lee . Interdigitated Hydrogen Bonds: Electrophile Activation for Covalent Capture and Fluorescence Turn-On Detection of Cyanide. Journal of the American Chemical Society 2013, 135
(9)
, 3620-3632. https://doi.org/10.1021/ja312313f
- Christian Ruthard, Michael Maskos, Ute Kolb, and Franziska Gröhn . Polystyrene Sulfonate–Porphyrin Assemblies: Influence of Polyelectrolyte and Porphyrin Structure. The Journal of Physical Chemistry B 2011, 115
(19)
, 5716-5729. https://doi.org/10.1021/jp1078357
- Tom F. A. de Greef, Marko M. L. Nieuwenhuizen, Rint P. Sijbesma and E. W. Meijer. Competitive Intramolecular Hydrogen Bonding in Oligo(ethylene oxide) Substituted Quadruple Hydrogen Bonded Systems. The Journal of Organic Chemistry 2010, 75
(3)
, 598-610. https://doi.org/10.1021/jo902053t
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(11)
, 3339-3354. https://doi.org/10.1021/jp8096605
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(7)
, 1469-1472. https://doi.org/10.1021/ol8002755
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(7)
, 3561-3565. https://doi.org/10.1021/la062339q
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(5)
, 985-997. https://doi.org/10.1002/cplu.202000142
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via
hierarchical self-assembly. Chemical Communications 2019, 55
(56)
, 8036-8059. https://doi.org/10.1039/C9CC02472G
- Bo Li, Tian He, Xi Shen, Danting Tang, Shouchun Yin. Fluorescent supramolecular polymers with aggregation induced emission properties. Polymer Chemistry 2019, 10
(7)
, 796-818. https://doi.org/10.1039/C8PY01396A
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(14)
https://doi.org/10.1002/adma.201606117
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(17)
, 4039-4045. https://doi.org/10.1039/C6OB00064A
- Yunshen Zhang, Yichao Huang, Jiangwei Zhang, Li Zhu, Kun Chen, Jian Hao. Two unprecedented aromatic guanidines supramolecular chains self-assembled by hydrogen bonding interaction. Journal of Molecular Structure 2015, 1097 , 145-150. https://doi.org/10.1016/j.molstruc.2015.05.024
- Hu Wang, Pi Wang, Hao Xing, Ning Li, Xiaofan Ji. A multistimuli‐responsive supramolecular polymer constructed by crown ether‐based molecular recognition and disulfide bond connection. Journal of Polymer Science Part A: Polymer Chemistry 2015, 53
(18)
, 2079-2084. https://doi.org/10.1002/pola.27693
- Wei Wang, Jun Gu, Xiaoliang Zou, Weiqi Tong, Hegui Gong. Solid state studies of the assembly of diionic guanidinium/carboxylate compounds. Tetrahedron Letters 2015, 56
(21)
, 2684-2687. https://doi.org/10.1016/j.tetlet.2015.03.123
- Christina Rest, Ramesh Kandanelli, Gustavo Fernández. Strategies to create hierarchical self-assembled structures via cooperative non-covalent interactions. Chemical Society Reviews 2015, 44
(8)
, 2543-2572. https://doi.org/10.1039/C4CS00497C
- Andrei K. Yudin. Macrocycles: lessons from the distant past, recent developments, and future directions. Chemical Science 2015, 6
(1)
, 30-49. https://doi.org/10.1039/C4SC03089C
- Chunlin Lv, Junjie Hu, Rao Naumaan Nasim Khan, Jin Zhang, Yongge Wei. Postfunctionalization of polyoxometalates: an efficient strategy to construct organic–inorganic zwitterions. Dalton Transactions 2015, 44
(38)
, 16698-16702. https://doi.org/10.1039/C5DT02407B
- Ángel M. Valdivielso, Alba Catot, Ignacio Alfonso, Ciril Jimeno. Intramolecular hydrogen bonding guides a cationic amphiphilic organocatalyst to highly stereoselective aldol reactions in water. RSC Advances 2015, 5
(77)
, 62331-62335. https://doi.org/10.1039/C5RA12135C
- Yosuke Hisamatsu, Supratim Banerjee, M. B. Avinash, T. Govindaraju, Carsten Schmuck. A Supramolecular Gel from a Quadruple Zwitterion that Responds to Both Acid and Base. Angewandte Chemie 2013, 125
(48)
, 12782-12786. https://doi.org/10.1002/ange.201306986
- Yosuke Hisamatsu, Supratim Banerjee, M. B. Avinash, T. Govindaraju, Carsten Schmuck. A Supramolecular Gel from a Quadruple Zwitterion that Responds to Both Acid and Base. Angewandte Chemie International Edition 2013, 52
(48)
, 12550-12554. https://doi.org/10.1002/anie.201306986
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(36)
, 11892-11897. https://doi.org/10.1002/chem.201301022
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(1)
, 84-87. https://doi.org/10.1002/asia.201200881
- Shengyi Dong, Lingyan Gao, Jianzhuang Chen, Guocan Yu, Bo Zheng, Feihe Huang. A supramolecular polymer formed by the combination of crown ether-based and charge-transfer molecular recognition. Polym. Chem. 2013, 4
(4)
, 882-886. https://doi.org/10.1039/C2PY21028B
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(9)
, 2767. https://doi.org/10.1039/c3py00201b
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(11)
, 3312. https://doi.org/10.1039/c3py00283g
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(14)
, 3998. https://doi.org/10.1039/c3py00462g
- Yoram Cohen, Liat Avram, Tamar Evan‐Salem, Sarit Slovak, Noam Shemesh, Limor Frish. Diffusion NMR in Supramolecular Chemistry and Complexed Systems. 2012, 197-285. https://doi.org/10.1002/9783527644131.ch6
- Tassilo Fenske, Hans‐Gert Korth, Andreas Mohr, Carsten Schmuck. Advances in Switchable Supramolecular Nanoassemblies. Chemistry – A European Journal 2012, 18
(3)
, 738-755. https://doi.org/10.1002/chem.201102435
- Thomas H. Rehm, Franziska Gröhn, Carsten Schmuck. Self-assembly of a triple-zwitterion in polar solutions: hierarchical formation of nanostructures. Soft Matter 2012, 8
(11)
, 3154. https://doi.org/10.1039/c2sm07153c
- Karsten Meyenberg, Antonina S. Lygina, Geert van den Bogaart, Reinhard Jahn, Ulf Diederichsen. SNARE derived peptide mimic inducing membrane fusion. Chemical Communications 2011, 47
(33)
, 9405. https://doi.org/10.1039/c1cc12879e
- Fabian Rodler, Jürgen Linders, Tassilo Fenske, Thomas Rehm, Christian Mayer, Carsten Schmuck. pH‐schaltbare Vesikel aus einem von Serin abgeleiteten Guanidiniocarbonylpyrrol‐Carboxylat‐Zwitterion in DMSO. Angewandte Chemie 2010, 122
(46)
, 8929-8932. https://doi.org/10.1002/ange.201003405
- Fabian Rodler, Jürgen Linders, Tassilo Fenske, Thomas Rehm, Christian Mayer, Carsten Schmuck. pH‐Switchable Vesicles from a Serine‐Derived Guanidiniocarbonyl Pyrrole Carboxylate Zwitterion in DMSO. Angewandte Chemie International Edition 2010, 49
(46)
, 8747-8750. https://doi.org/10.1002/anie.201003405
- Pavel A. Belyakov, Valentine I. Kadentsev, Alexander O. Chizhov, Natal’ya G. Kolotyrkina, Alexander S. Shashkov, Valentine P. Ananikov. Mechanistic insight into organic and catalytic reactions by joint studies using mass spectrometry and NMR spectroscopy. Mendeleev Communications 2010, 20
(3)
, 125-131. https://doi.org/10.1016/j.mencom.2010.05.001
- Ignacio Alfonso, Miriam Bru, M. Isabel Burguete, Eduardo García‐Verdugo, Santiago V. Luis. Structural Diversity in the Self‐Assembly of Pseudopeptidic Macrocycles. Chemistry – A European Journal 2010, 16
(4)
, 1246-1255. https://doi.org/10.1002/chem.200902196
- Hiromitsu Maeda. Acyclic Oligopyrrolic Anion Receptors. 2010, 103-143. https://doi.org/10.1007/7081_2010_32
- Thomas H. Rehm, Carsten Schmuck. Ion-pair induced self-assembly in aqueous solvents. Chemical Society Reviews 2010, 39
(10)
, 3597. https://doi.org/10.1039/b926223g
- Carolin Rether, Wilhelm Sicking, Roland Boese, Carsten Schmuck. Self-association of an indole based guanidinium-carboxylate-zwitterion: formation of stable dimers in solution and the solid state. Beilstein Journal of Organic Chemistry 2010, 6 https://doi.org/10.3762/bjoc.6.3
- Ümit Hakan Yildiz, Kaloian Koynov, Franziska Gröhn. Fluorescent Nanoparticles through Self‐Assembly of Linear Ionenes and Pyrenetetrasulfonate. Macromolecular Chemistry and Physics 2009, 210
(20)
, 1678-1690. https://doi.org/10.1002/macp.200900224
- Franziska Gröhn. Electrostatic Self‐Assembly as Route to Supramolecular Structures. Macromolecular Chemistry and Physics 2008, 209
(22)
, 2295-2301. https://doi.org/10.1002/macp.200800290
- Immanuel Willerich, Franziska Gröhn. Switchable Nanoassemblies from Macroions and Multivalent Dye Counterions. Chemistry – A European Journal 2008, 14
(30)
, 9112-9116. https://doi.org/10.1002/chem.200801167
- Anne de Cuendias, Emmanuel Ibarboure, Sébastien Lecommandoux, Eric Cloutet, Henri Cramail. Synthesis and self‐assembly in water of coil‐rod‐coil amphiphilic block copolymers with central π‐conjugated sequence. Journal of Polymer Science Part A: Polymer Chemistry 2008, 46
(13)
, 4602-4616. https://doi.org/10.1002/pola.22793
- Elena Lestini, Kirill Nikitin, Helge Müller‐Bunz, Donald Fitzmaurice. Introducing Negative Charges into Bis‐
p
‐phenylene Crown Ethers: A Study of Bipyridinium‐Based [2]Pseudorotaxanes and [2]Rotaxanes. Chemistry – A European Journal 2008, 14
(4)
, 1095-1106. https://doi.org/10.1002/chem.200700387
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N
‐Protected 5‐(Guanidinocarbonyl)‐1
H
‐pyrrole‐2‐carboxylic Acids. European Journal of Organic Chemistry 2008, 2008
(2)
, 324-329. https://doi.org/10.1002/ejoc.200700756
- Thomas Rehm, Carsten Schmuck. How to achieve self-assembly in polar solvents based on specific interactions? Some general guidelines. Chem. Commun. 2008, 110
(7)
, 801-813. https://doi.org/10.1039/B710951M
- Carsten Schmuck, Daniel Rupprecht, Matthias Junkers, Thomas Schrader. Artificial Ditopic Arg‐Gly‐Asp (RGD) Receptors. Chemistry – A European Journal 2007, 13
(24)
, 6864-6873. https://doi.org/10.1002/chem.200601821
- Carsten Schmuck, Jürgen Dudaczek. Ion Pairing Between the Chain Ends Induces Folding of a Flexible Zwitterion in Methanol. European Journal of Organic Chemistry 2007, 2007
(20)
, 3326-3330. https://doi.org/10.1002/ejoc.200700164
- Carsten Schmuck, Thomas Rehm, Katja Klein, Franziska Gröhn. Formation of Vesicular Structures through the Self‐Assembly of a Flexible Bis‐Zwitterion in Dimethyl Sulfoxide. Angewandte Chemie 2007, 119
(10)
, 1723-1727. https://doi.org/10.1002/ange.200603629
- Carsten Schmuck, Thomas Rehm, Katja Klein, Franziska Gröhn. Formation of Vesicular Structures through the Self‐Assembly of a Flexible Bis‐Zwitterion in Dimethyl Sulfoxide. Angewandte Chemie International Edition 2007, 46
(10)
, 1693-1697. https://doi.org/10.1002/anie.200603629