Mixed-Valent Click Intertwined Polymer Units Containing Biferrocenium Chloride Side Chains Form Nanosnakes that Encapsulate Gold Nanoparticles
- Amalia Rapakousiou ,
- Christophe Deraedt ,
- Haibin Gu ,
- Lionel Salmon ,
- Colette Belin ,
- Jaime Ruiz , and
- Didier Astruc
Abstract

Polymers containing triazolylbiferrocene are synthesized by ROMP or radical chain reactions and react with HAuCl4 to provide class-2 mixed-valent triazolylbiferrocenium polyelectrolyte networks (observed inter alia by TEM and AFM) that encapsulate gold nanoparticles (AuNPs). With triazolylbiferrocenium in the side polymer chain, the intertwined polymer networks form nanosnakes, unlike with triazolylbiferrocenium in the main polymer chain. By contrast, simple ferrocene-containing polymers do not form such a ferricenium network upon reaction with AuIII, but only small AuNPs, showing that the triazolyl ligand, the cationic charge, and the biferrocenium structure are coresponsible for such network formations.
Cited By
This article is cited by 36 publications.
- Haibin Gu, Roberto Ciganda, Patricia Castel, Jaime Ruiz, and Didier Astruc . Living ROMP Syntheses and Redox Properties of Triblock Metallocopolymer Redox Cascades. Macromolecules 2016, 49 (13) , 4763-4773. https://doi.org/10.1021/acs.macromol.6b01046
- Sebastiano Guerra, Thi Le Anh Nguyen, Julien Furrer, Jean-François Nierengarten, Joaquín Barberá, and Robert Deschenaux . Liquid-Crystalline Dendrimers Designed by Click Chemistry. Macromolecules 2016, 49 (9) , 3222-3231. https://doi.org/10.1021/acs.macromol.6b00432
- Jiawei Chen, Didier A. Murillo Parra, Roger A. Lalancette, and Frieder Jäkle . Redox-Switchable Chiral Anions and Cations Based on Heteroatom-Fused Biferrocenes. Organometallics 2015, 34 (17) , 4323-4330. https://doi.org/10.1021/acs.organomet.5b00577
- Amalia Rapakousiou, Christophe Deraedt, Joseba Irigoyen, Yanlan Wang, Noël Pinaud, Lionel Salmon, Jaime Ruiz, Sergio Moya, and Didier Astruc . Synthesis and Redox Activity of “Clicked” Triazolylbiferrocenyl Polymers, Network Encapsulation of Gold and Silver Nanoparticles and Anion Sensing. Inorganic Chemistry 2015, 54 (5) , 2284-2299. https://doi.org/10.1021/ic5028916
- Xiong Liu, Fangfei Liu, Wentao Liu, Haibin Gu. ROMP and MCP as Versatile and Forceful Tools to Fabricate Dendronized Polymers for Functional Applications. Polymer Reviews 2021, 61 (1) , 1-53. https://doi.org/10.1080/15583724.2020.1723022
- Didier Astruc. The supramolecular redox functions of metallomacromolecules. Journal of Leather Science and Engineering 2020, 2 (1) https://doi.org/10.1186/s42825-020-00026-z
- Xiong Liu, Amalia Rapakousiou, Christophe Deraedt, Roberto Ciganda, Yanlan Wang, Jaime Ruiz, Haibin Gu, Didier Astruc. Multiple applications of polymers containing electron-reservoir metal-sandwich complexes. Chemical Communications 2020, 56 (77) , 11374-11385. https://doi.org/10.1039/D0CC04586A
- Xiong Liu, Li Zhao, Fangfei Liu, Didier Astruc, Haibin Gu. Supramolecular redox-responsive ferrocene hydrogels and microgels. Coordination Chemistry Reviews 2020, 419 , 213406. https://doi.org/10.1016/j.ccr.2020.213406
- Yanru Long, Bin Song, Chutong Shi, Wentao Liu, Haibin Gu. AuNPs composites of gelatin hydrogels crosslinked by ferrocene‐containing polymer as recyclable supported catalysts. Journal of Applied Polymer Science 2020, 137 (19) , 48653. https://doi.org/10.1002/app.48653
- Didier Astruc. Design and Functions of Macromolecular Electron-Reservoir Complexes and Devices. Journal of Inorganic and Organometallic Polymers and Materials 2020, 30 (1) , 111-120. https://doi.org/10.1007/s10904-019-01412-9
- Xiong Liu, Fangfei Liu, Yanlan Wang, Haibin Gu. Ferrocene-containing amphiphilic dendronized random copolymer as efficient stabilizer for reusable gold nanoparticles in catalysis. Reactive and Functional Polymers 2019, 143 , 104325. https://doi.org/10.1016/j.reactfunctpolym.2019.104325
- Guirong Qiu, Xiong Liu, Binrong Wang, Haibin Gu, Weixiang Wang. Ferrocene-containing amphiphilic polynorbornenes as biocompatible drug carriers. Polymer Chemistry 2019, 10 (20) , 2527-2539. https://doi.org/10.1039/C9PY00332K
- Xiong Liu, Fangfei Liu, Didier Astruc, Wei Lin, Haibin Gu. Highly-branched amphiphilic organometallic dendronized diblock copolymer: ROMP synthesis, self-assembly and long-term Au and Ag nanoparticle stabilizer for high-efficiency catalysis. Polymer 2019, 173 , 1-10. https://doi.org/10.1016/j.polymer.2019.04.021
- Shengdong Mu, Wentao Liu, Li Zhao, Yanru Long, Haibin Gu. Antimicrobial AgNPs composites of gelatin hydrogels crosslinked by ferrocene-containing tetrablock terpolymer. Polymer 2019, 169 , 80-94. https://doi.org/10.1016/j.polymer.2019.02.047
- Arefe Salamatmanesh, Maryam Kazemi Miraki, Elahe Yazdani, Akbar Heydari. Copper(I)–Caffeine Complex Immobilized on Silica-Coated Magnetite Nanoparticles: A Recyclable and Eco-friendly Catalyst for Click Chemistry from Organic Halides and Epoxides. Catalysis Letters 2018, 148 (10) , 3257-3268. https://doi.org/10.1007/s10562-018-2523-0
- Yue Liu, Shengdong Mu, Xiong Liu, Qiangjun Ling, Chaodong Hang, Jaime Ruiz, Didier Astruc, Haibin Gu. Ferrocenyl Janus mixed-dendron stars and their stabilization of Au and Ag nanoparticles. Tetrahedron 2018, 74 (37) , 4777-4789. https://doi.org/10.1016/j.tet.2018.07.035
- Didier Astruc, Christophe Deraedt, Rodrigue Djeda, Catia Ornelas, Xiang Liu, Amalia Rapakousiou, Jaime Ruiz, Yanlan Wang, Qi Wang. Dentromers, a Family of Super Dendrimers with Specific Properties and Applications. Molecules 2018, 23 (4) , 966. https://doi.org/10.3390/molecules23040966
- Li Zhao, Qiangjun Ling, Xiong Liu, Chaodong Hang, Qiuxia Zhao, Fangfei Liu, Haibin Gu. Multifunctional triazolylferrocenyl Janus dendron: Nanoparticle stabilizer, smart drug carrier and supramolecular nanoreactor. Applied Organometallic Chemistry 2018, 32 (2) https://doi.org/10.1002/aoc.4000
- Ileana Dragutan, Valerian Dragutan, Albert Demonceau. Organometallic Polymers by Ring-Opening Metathesis Polymerization (ROMP) Reactions. 2018,,https://doi.org/10.1016/B978-0-12-409547-2.14232-5
- Amalia Rapakousiou, Ryota Sakamoto, Ryo Shiotsuki, Ryota Matsuoka, Ukyo Nakajima, Tigmansu Pal, Rintaro Shimada, Amran Hossain, Hiroyasu Masunaga, Satoshi Horike, Yasutaka Kitagawa, Sono Sasaki, Kenichi Kato, Takeaki Ozawa, Didier Astruc, Hiroshi Nishihara. Liquid/Liquid Interfacial Synthesis of a Click Nanosheet. Chemistry - A European Journal 2017, 23 (35) , 8443-8449. https://doi.org/10.1002/chem.201700201
- Didier Astruc. Why is Ferrocene so Exceptional?. European Journal of Inorganic Chemistry 2017, 2017 (1) , 6-29. https://doi.org/10.1002/ejic.201600983
- Amalia Rapakousiou, Colette Belin, Lionel Salmon, Jaime Ruiz, Didier Astruc. Click Co sandwich-terminated dendrimers as polyhydride reservoirs and micellar templates. Chemical Communications 2017, 53 (46) , 6267-6270. https://doi.org/10.1039/C7CC03311G
- J. Song, Y. N. Tan, D. Jańczewski, M. A. Hempenius, J. W. Xu, H. R. Tan, G. J. Vancso. Poly(ferrocenylsilane) electrolytes as a gold nanoparticle foundry: “two-in-one” redox synthesis and electrosteric stabilization, and sensing applications. Nanoscale 2017, 9 (48) , 19255-19262. https://doi.org/10.1039/C7NR04697A
- James W. Herndon. The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014. Coordination Chemistry Reviews 2016, 317 , 1-121. https://doi.org/10.1016/j.ccr.2015.09.012
- Haibin Gu, Roberto Ciganda, Ricardo Hernández, Patricia Castel, Amélie Vax, Pengxiang Zhao, Jaime Ruiz, Didier Astruc. Diblock metallocopolymers containing various iron sandwich complexes: living ROMP synthesis and selective reversible oxidation. Polymer Chemistry 2016, 7 (13) , 2358-2371. https://doi.org/10.1039/C6PY00202A
- Shengyang Tao, Huan Wang, Huilong Wang. Preparing highly-dispersed noble metal supported mesoporous silica catalysts by reductive amphiphilic molecules. RSC Advances 2016, 6 (113) , 112193-112200. https://doi.org/10.1039/C6RA23875K
- Haibin Gu, Roberto Ciganda, Patricia Castel, Amélie Vax, Danijela Gregurec, Joseba Irigoyen, Sergio Moya, Lionel Salmon, Pengxiang Zhao, Jaime Ruiz, Ricardo Hernández, Didier Astruc. Redox-Robust Pentamethylferrocene Polymers and Supramolecular Polymers, and Controlled Self-Assembly of Pentamethylferricenium Polymer-Embedded Ag, AgI, and Au Nanoparticles. Chemistry - A European Journal 2015, 21 (50) , 18177-18186. https://doi.org/10.1002/chem.201503248
- Ziyin Fan, Xuelian Chen, Melissa Köhn Serrano, Holger Schmalz, Sabine Rosenfeldt, Stephan Förster, Seema Agarwal, Andreas Greiner. Polymerkäfige als universelles Hilfsmittel für die präzise Bottom-up-Synthese metallischer Nanopartikel. Angewandte Chemie 2015, 127 (48) , 14747-14752. https://doi.org/10.1002/ange.201506415
- Ziyin Fan, Xuelian Chen, Melissa Köhn Serrano, Holger Schmalz, Sabine Rosenfeldt, Stephan Förster, Seema Agarwal, Andreas Greiner. Polymer Cages as Universal Tools for the Precise Bottom‐Up Synthesis of Metal Nanoparticles. Angewandte Chemie International Edition 2015, 54 (48) , 14539-14544. https://doi.org/10.1002/anie.201506415
- Ileana Dragutan, Valerian Dragutan, Albert Demonceau. Editorial of Special Issue Ruthenium Complex: The Expanding Chemistry of the Ruthenium Complexes. Molecules 2015, 20 (9) , 17244-17274. https://doi.org/10.3390/molecules200917244
- Christophe Deraedt, Amalia Rapakousiou, Haibin Gu, Lionel Salmon, Jaime Ruiz, Didier Astruc. Catalytically-Active Palladium Nanoparticles Stabilized by Triazolylbiferrocenyl-Containing Polymers. Journal of Inorganic and Organometallic Polymers and Materials 2015, 25 (3) , 437-446. https://doi.org/10.1007/s10904-014-0161-6
- Didier Astruc, Jaime Ruiz. On the Redox Chemistry of Ferrocenes and Other Iron Sandwich Complexes and Its Applications. Journal of Inorganic and Organometallic Polymers and Materials 2015, 25 (3) , 330-338. https://doi.org/10.1007/s10904-015-0178-5
- Yiming Li, Zhilong Jiang, Jie Yuan, Die Liu, Tun Wu, Charles N. Moorefield, George R. Newkome, Pingshan Wang. Facile thermodynamic conversion of a linear metallopolymer into a self-assembled hexameric metallomacrocycle. Chemical Communications 2015, 51 (26) , 5766-5769. https://doi.org/10.1039/C4CC10361K
- Saverio Santi, Annalisa Bisello, Roberta Cardena, Alessandro Donoli. Key multi(ferrocenyl) complexes in the interplay between electronic coupling and electrostatic interaction. Dalton Transactions 2015, 44 (12) , 5234-5257. https://doi.org/10.1039/C4DT03581J
- Ileana Dragutan, Valerian Dragutan, Bogdan C Simionescu, Albert Demonceau, Helmut Fischer. Recent advances in metathesis-derived polymers containing transition metals in the side chain. Beilstein Journal of Organic Chemistry 2015, 11 , 2747-2762. https://doi.org/10.3762/bjoc.11.296
- Amalia Rapakousiou, Rodrigue Djeda, Maxime Grillaud, Na Li, Jaime Ruiz, Didier Astruc. “Click” Assemblies and Redox Properties of Arene- and Gold-Nanoparticle-Cored Triazolylbiferrocene-Terminated Dendrimers. Organometallics 2014, 33 (23) , 6953-6962. https://doi.org/10.1021/om501031u



