Supramolecular polymer networks crosslinked by crown ether-based host–guest recognition: dynamic materials with tailored mechanical properties in the bulk

Bai, Ruixue; Zhang, Hao; Yang, Xue; Zhao, Jun; Wang, Yongming; Zhang, Zhaoming; Yan, Xuzhou

doi:10.1039/d1py01536b

Cited by 18 publications

(12 citation statements)

References 56 publications

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“…(g) Comparison of characteristic relaxation time of conventional supramolecular materials with HFBA-1.5 M LiTFSI versus temperature. Supramolecular materials are based on hydrogen bonds, − coordination bonds, , ionic bonds, and host–guest interactions. , …”

Section: Resultsmentioning

confidence: 99%

Multivalent Design of Low-Entropy-Penalty Ion–Dipole Interactions for Dynamic Yet Thermostable Supramolecular Networks

et al. 2023

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Dynamic supramolecular networks are constantly accompanied by thermal instability. The fundamental reason is most reversible noncovalent bonds quickly decay at elevated temperatures and dissociate below 100 °C. Here, in this paper, we realize a reversible ion–dipole interaction with high-temperature stability exceeding 150 °C. The resultant supramolecular network can simultaneously possess mechanical strength of 1.32 MPa (14.8 times that of pristine material), dynamic self-healing capability, and a stable working temperature of up to 200 °C. From the prolonged characteristic relaxation time of 600 s even at 100 °C, our material represents one of the most thermally stable dynamic supramolecular polymers. These remarkable performances are achieved by using a new multivalent yet low-entropy-penalty molecular design. In this way, the noncovalent bond can reach a high enthalpy while minimizing the entropy-dominated thermal dissociations.

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Section: Resultsmentioning

confidence: 99%

Multivalent Design of Low-Entropy-Penalty Ion–Dipole Interactions for Dynamic Yet Thermostable Supramolecular Networks

et al. 2023

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“…The favorable stretchability of SPN-3 was displayed in Figure 2d. Moreover, the mechanical properties of SPN-3 were also compared with reported supramolecular polymer networks cross-linked through other types of host-guest interactions between charged or neutral guests and macrocyclic hosts including crown ethers, [14,26] cyclodextrins, [27] and pillararenes. [28] As shown in Figure 2d, in the aspects of maximum stress, toughness and Young's modulus, our SPN-3 exhibited certain advantages in contrast with other supramolecular polymer networks, which we believe to be associated with the contribution of strong cryptand-based supramolecular cross-links in our SPNs.…”

Section: Mechanical Properties Of the Spns And The Controlsmentioning

confidence: 99%

“…Therefore, although they have been exploited to develop some attractive dynamic materials, their mechanical performance fails to attain the abovementioned high levels, particularly in terms of the strength and stiffness. [14] In 1968, Simmons and co-workers synthesized the first cryptand in which an additional arm was introduced into the planar macrocyclic structure of a macrocycle to form a three-dimensional cave-shaped architecture. [15] As evolved derivatives of crown ethers, cryptands not only retain their intriguing dynamic features, but also possess ultrahigh association constants which are generally 10 2 -10 3 folds higher than those of their analogous crown ethers due to their specific properties of multi-cavity structures, multi-binding sites, and multi-complexation modes.…”

Section: Introductionmentioning

confidence: 99%

Highly Strong and Tough Supramolecular Polymer Networks Enabled by Cryptand‐Based Host‐Guest Recognition

et al. 2023

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Supramolecular polymer networks (SPNs) demonstrate great potential in the development of smart materials owing to their attractive dynamic properties. However, as they suffer from the inherent weak bonding of most noncovalent cross‐links, it remains a significant challenge to construct SPNs with outstanding mechanical performance. Herein, we exploit the cryptand/paraquat host‐guest recognition motifs as cross‐links to prepare a class of highly strong and tough SPNs. Unlike those supramolecular cross‐links with relatively weak binding abilities, the cryptand‐based host‐guest interactions have a high association constant and steady complexing structure, which effectively stabilizes the network and resists mechanical deformation under external force. Such favorable structural stability endows our SPNs with greatly enhanced mechanical performance, compared with the control‐1 cross‐linked by the weakly complexed crown ether/secondary ammonium salt motif (tensile strength: 21.1±0.5 vs 2.8±0.1 MPa; Young's modulus: 102.6±4.8 vs 2.1±0.3 MPa; toughness: 90.4±2.0 vs 10.8±0.6 MJ m−3). Moreover, our SPNs also retain abundant dynamic properties including good abilities in energy dissipation, reprocessability, and stimuli‐responsiveness. These findings provide novel insights into the preparation of SPNs with enhanced mechanical properties, and promote the development of high‐performance intelligent supramolecular materials.

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“…Supramolecular gels are an important class of self-healable materials due to the reversible noncovalent interactions within the networked structures. − Supramolecular gels derived from metal–organic polymers displaying electrical conductivity have shown numerous application potential. ,, The reversible nature of coordination bonds between the organic ligands and the metal ions make them promising alternatives to prepare new self-healable gel electrolytes. − Herein, we report a new hybrid gel electrolyte based on a designed supramolecular metal–organic gel (MOG) and PVA, along with its proof-of-concept demonstration in flexible capacitor sensing. Stabilized by cooperative coordination bonding and intra-/intermolecular hydrogen bonding between the MOG and PVA, the hybrid gel shows not only excellent shape-preserving and self-healable properties but also good performance when applying this hybrid gel as electrolyte in a printed interdigital capacitor (IDC) sensor.…”

Section: Introductionmentioning

confidence: 99%

Self-Healable Poly(vinyl alcohol)─Metal–Organic Hybrid Gel Electrolyte for Flexible Capacitor Sensors

Wang

Zhang

Zhou

et al. 2022

ACS Appl. Polym. Mater.

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Supramolecular gels based on noncovalent interaction are attractive self-healable polymeric electrolytes due to their repeatable spontaneous recovery of mechanical and electrochemical performance. Herein, we report such a hybrid supramolecular gel electrolyte system composed of a poly(vinyl alcohol) (PVA)–palladium-coordination metal–organic gel (MOG) by controlling ligand conformation transition from cis to trans. The reversible coordination and hydrogen bonding interactions endow the PVA/MOG hybrid gels with 17 consecutive self-healing in 10000S and ultrafast self-healable ability in both mechanical and electrochemical time scales of 180 and 60 s, respectively. The polyaniline (PANI)-based printed interdigital capacitor (IDC) sensor with the hybrid gel electrolyte exhibits a wide voltage window of 0–2.75 V, stable charge–discharge cycle at a high scan rate of 500 mV/s. When printed onto a glove, our sensor can recognize the hand fist and open with good sensitivity. This work provides a promising direction for designing flexible capacitor sensors with self-healable MOGs.

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Supramolecular polymer networks crosslinked by crown ether-based host–guest recognition: dynamic materials with tailored mechanical properties in the bulk

Abstract: Supramolecular polymer networks (SPNs) based on host-guest recognition have attracted much research attention to develop smart supramolecular materials. However, these researches mainly focus on SPNs in solution or in gel...

Cited by 18 publications

References 56 publications

Multivalent Design of Low-Entropy-Penalty Ion–Dipole Interactions for Dynamic Yet Thermostable Supramolecular Networks

Multivalent Design of Low-Entropy-Penalty Ion–Dipole Interactions for Dynamic Yet Thermostable Supramolecular Networks

Highly Strong and Tough Supramolecular Polymer Networks Enabled by Cryptand‐Based Host‐Guest Recognition

Self-Healable Poly(vinyl alcohol)─Metal–Organic Hybrid Gel Electrolyte for Flexible Capacitor Sensors

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