Pathway Complexity in Nanotubular Supramolecular Polymerization: Metal–Organic Nanotubes with a Planar-Chiral MonomerClick to copy article linkArticle link copied!
- Yingluo ZhaoYingluo ZhaoDepartment of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, JapanRIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanMore by Yingluo Zhao
- Hiroko KawanoHiroko KawanoDepartment of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, JapanMore by Hiroko Kawano
- Hiroshi Yamagishi*Hiroshi Yamagishi*[email protected] (H.Y.)Department of Materials Science, Faculty of Pure and Applied Sciences, and Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, JapanMore by Hiroshi Yamagishi
- Saya OtakeSaya OtakeDepartment of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, JapanMore by Saya Otake
- Yoshimitsu ItohYoshimitsu ItohDepartment of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, JapanMore by Yoshimitsu Itoh
- Hubiao HuangHubiao HuangRIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanMore by Hubiao Huang
- E. W. MeijerE. W. MeijerInstitute for Complex Molecular Systems (ICMS) and Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, 5600 MB Eindhoven, The NetherlandsMore by E. W. Meijer
- Takuzo Aida*Takuzo Aida*[email protected] (T.A.)Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, JapanRIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanMore by Takuzo Aida
Abstract
Here, we report an anomalous pathway complexity in the supramolecular polymerization of a chiral monomer, which displays an unusual chiroptical feature that does not follow any of the known stereochemical rules such as “chiral self-sorting” and “majority rule”. We newly developed a planar-chiral ferrocene-cored tetratopic pyridyl monomer FcL, which underwent AgBF4-mediated supramolecular polymerization to give nanotubes FcNTs composed of metal–organic nanorings FcNRs. Although FcNRs must be homochiral because of a strong geometrical constraint, FcNRs were formed even efficiently from racemic FcL and AgBF4. Detailed studies revealed the presence of two competing pathways for producing homochiral FcNRs as the constituents of FcNTs: (i) spontaneous cyclization of initially formed acyclic polymers -[FcL-Ag+]n- and (ii) template (FcNR)-assisted cyclization via a Ag+···Ag+ metallophilic interaction. The dominance of the two pathways changes depending on the %ee of chiral FcL. Namely, when the %ee of FcL is high, -[FcL-Ag+]n- must contain sufficiently long homochiral sequences that can be readily cyclized into FcNRs. Meanwhile, when the %ee of FcL is low, the homochiral sequences in -[FcL-Ag+]n- must be short and therefore are hardly eligible for spontaneous cyclization. Why were FcNRs formed? Even though the probability is very low, homochiral -[FcL-Ag+]n- can be statistically generated and undergo spontaneous cyclization to give FcNRs minutely. We found that FcNRs can be amplified by heterochirally templating their own synthesis using metallophilic interaction. Because of this stereochemical preference, the growth of FcNRs into FcNTs via the template-assisted mechanism occurs only when both (R,R)FcL and (S,S)FcL are present in the polymerization system.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 8 publications.
- Lishan Sun, Chenglong Liao, Zihua Zhu, Yangyang Ren, Ran Duan, Hongwei Ji, Ling Zang, Yanke Che, Jincai Zhao. Lockable Multiple Twisting in Donor–Acceptor Molecules for Emergent Crystalline Structures and Optical Properties. Chemistry of Materials 2025, 37
(4)
, 1570-1577. https://doi.org/10.1021/acs.chemmater.4c03183
- Sayantan Mahapatra, Dingwen Qian, Ruihua Zhang, Shuliang Yang, Penghao Li, Yuanning Feng, Long Zhang, Huang Wu, James S. W. Seale, Partha Jyoti Das, Prateek K. Jha, Kevin Lee Kohlstedt, Monica Olvera de la Cruz, J. Fraser Stoddart. Hydrogen-Bonded Fibrous Nanotubes Assembled from Trigonal Prismatic Building Blocks. Journal of the American Chemical Society 2024, 146
(31)
, 21689-21699. https://doi.org/10.1021/jacs.4c05804
- Jia-Ge Jia, Chen-Chen Zhao, Yi-Fan Wei, Zhi-Min Zhai, Song-Song Bao, Allan J. Jacobson, Jing Ma, Li-Min Zheng. Macroscopic Helical Assembly of One-Dimensional Coordination Polymers: Helicity Inversion Triggered by Solvent Isomerism. Journal of the American Chemical Society 2023, 145
(44)
, 23948-23962. https://doi.org/10.1021/jacs.3c05552
- Ya-Nan Du, Ya-Nan Pan, Xian-Hui Du, Chen-Chen Ye, Chao Wang, Man-Yi Han, Lei Xu. Facile synthesis and controlled self-assembly of poly(phenyl isocyanide)-
block
-polycarbonate copolymers. Polymer Chemistry 2024, 15
(36)
, 3667-3674. https://doi.org/10.1039/D4PY00800F
- Payel Khanra, Priya Rajdev, Anindita Das. Seed‐Induced Living Two‐Dimensional (2D) Supramolecular Polymerization in Water: Implications on Protein Adsorption and Enzyme Inhibition. Angewandte Chemie 2024, 136
(15)
https://doi.org/10.1002/ange.202400486
- Payel Khanra, Priya Rajdev, Anindita Das. Seed‐Induced Living Two‐Dimensional (2D) Supramolecular Polymerization in Water: Implications on Protein Adsorption and Enzyme Inhibition. Angewandte Chemie International Edition 2024, 63
(15)
https://doi.org/10.1002/anie.202400486
- Katsuhiko Ariga, Jingwen Song, Kohsaku Kawakami. Layer-by-layer designer nanoarchitectonics for physical and chemical communications in functional materials. Chemical Communications 2024, 60
(16)
, 2152-2167. https://doi.org/10.1039/D3CC04952C
- Chandrakanta Guchhait, Vembanan Suriyaa, Nihar Sahu, Sovik Dey Sarkar, Bimalendu Adhikari. Ferrocene: an exotic building block for supramolecular assemblies. Chemical Communications 2023, 59
(98)
, 14482-14496. https://doi.org/10.1039/D3CC03659F
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.