Three layered cucurbit[6]uril-based metal–organic rotaxane networks functionalized by sulfonic groups for proton conduction

Xu, Yan-Jun; Fan, Mingyue; Feng, Zhen-Jie; Li, Jun; Wu, Xue-Song; Sun, Jing; Wang, Xinlong; Su, Zhong‐Min

doi:10.1039/d2dt01283a

Cited by 7 publications

(2 citation statements)

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“…17 The high conductivity of MOF is due to the strong hydrogenbonding network in MOF that enables efficient proton transfer. 18 The current strategies to improve proton conductivity are as follows: using acid organic ligands with high proton carrier; 19 grafting acidic and hydrophilic functional groups onto the primitive framework; 20 and introducing guest species into the cavity to build more hydrogen bonds. 21 However, it has limitations, such as structural instability, complex structural characterization, and complicated proton conduction mechanism.…”

Section: ■ Introductionmentioning

confidence: 99%

SCSC Transformation and Post-Synthesis Modification of MOFs with Proton Conduction and Ratiometric Fluorescence-Sensing Properties

et al. 2023

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The modification of metal–organic framework (MOF) materials to facilitate their practical applications is an extremely challenging and meaningful topic. In this work, two stepwise modification strategies for MOFs were conducted. First, we have demonstrated a single-crystal-to-single-crystal (SCSC) transformation from a microporous three-dimensional (3D) MOF to a two-dimensional (2D) coordination polymer (CP). The centrosymmetric [Cd(3-bpdb)(MeO-ip)] n (1) transforms into a chiral [Cd2(3-bpdb)(MeO-ip)2(CH3OH)2] n (2), which is triggered by the reaction time with methanol that acts as a structure-directing agent. The conversion relationship of 1 to 2 at different reaction times was studied in detail. Density functional theory (DFT) calculations clearly state that the irreversible formation of 2 is thermodynamically favorable. Intriguingly, 2 exhibits good proton conduction of 1.34 × 10–3 S cm–1 under 363 K and 98% relative humidity (RH) due to unique H-bond network characteristics. To the best of our knowledge, there are very few cases of 3D to 2D SCSC transformation stimulated by reaction time. The results have important implications for understanding the SCSC transformation mechanism and synthetic chemistry. On the other hand, the lanthanide3+-functionalized hybrids (Ln3+-MOF), Ln3+@1, were continuously prepared by incorporating luminescent Ln3+ ions into the structure of 1 through encapsulating post-synthesis modification (PSM). Tb3+@1 exhibits double emission in water and shows visual ratiometric fluorescence behavior for sensing glutamic acid (Glu), tryptophan (Trp), and Al3+, which is more reliable and accurate than single emission. Our work may not only provide new insights into the multiple modification of MOF materials but also promote the practical application of such materials.

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Section: ■ Introductionmentioning

confidence: 99%

SCSC Transformation and Post-Synthesis Modification of MOFs with Proton Conduction and Ratiometric Fluorescence-Sensing Properties

et al. 2023

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“…Metal-organic frameworks (MOFs) are promising crystalline porous materials, which are self-assembled by metal ions or clusters and organic linkers containing binding sites. [16][17][18][19][20] Due to their structural diversity and designability, ultra-high specific surface area and chemical stability, [21][22][23] MOFs have been applied in many fields, such as magnetism, 24,25 catalysis, 26 fluorescence sensing, [27][28][29][30][31][32] gas adsorption and storage, [33][34][35][36] proton conduction, [37][38][39][40][41][42] etc. Among many applications, luminescent MOFs (LMOFs) based on transition metals have attracted wide attention due to their low cost and potential as a simple and effective fluorescent sensing material.…”

Section: àmentioning

confidence: 99%

Two new transition metal–organic frameworks as multiresponsive fluorescence sensors for detecting Fe³⁺, Cr₂O₇²⁻ and TNP

Feng

et al. 2022

New J. Chem.

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Dual Response to Light and Heat of a Metal–Organic Rotaxane Network Featuring Flexible Viologen‐Derived Structs

Jin

Meng

Zhang

et al. 2023

Adv Funct Materials

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Metal–organic rotaxane compounds (MORCs) with supramolecular (pseudo)rotaxane motifs as main structures have inherent dynamic character, but their potential as responsive molecular machines is largely hampered by poor responsiveness to external stimuli. In this study, using a multi‐functionalized pseudorotaxane linker that combines two kinds of functionalities, a novel MORC, U‐bpybc‐CB8 (U refers to uranyl, bpybc refers to 1, 1’‐bis(4‐carboxybenzyl)‐4, 4’‐bipyridinium, and CB8 is cucurbit[8]uril), with multi‐responsive capability that can respond to both light and thermal stimuli, is reported. The characterization, combining spectra measurements and single‐crystal X‐ray diffraction, shows that, due to the involvement of viologen‐functionalized flexible organic dicarboxylate guest molecule in the CB8‐ involved pseudorotaxane ligand, the resultant uranyl‐based MORC exhibits photochromic behavior after UV or visible light irradiation. More interestingly, it is revealed that the exceptional thermal response of U‐bpybc‐CB8 as temperature increases from 170 to 270 K, i.e., volume expansion followed by contraction after the inflection temperature of ≈230 K, can be stemmed from the lattice flexibility of this metal–organic supramolecular network. The dual responsiveness of MORCs reported here demonstrates the potential of such supramolecular assemblies as smart molecular components like sensors and switches that respond to light irradiation or temperature changes.

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Three layered cucurbit[6]uril-based metal–organic rotaxane networks functionalized by sulfonic groups for proton conduction

Abstract: Three new cucurbit[6]uril (CB[6])-based metal-organic rotaxane networks (MORNs) (named as CUST-711, CUST-712, CUST-713) functionalized by sulfonic group (-SO3H) have been designed and synthesized via hydrothermal method. All three compounds exhibited...

Cited by 7 publications

References 48 publications

SCSC Transformation and Post-Synthesis Modification of MOFs with Proton Conduction and Ratiometric Fluorescence-Sensing Properties

SCSC Transformation and Post-Synthesis Modification of MOFs with Proton Conduction and Ratiometric Fluorescence-Sensing Properties

Two new transition metal–organic frameworks as multiresponsive fluorescence sensors for detecting Fe³⁺, Cr₂O₇²⁻ and TNP

Dual Response to Light and Heat of a Metal–Organic Rotaxane Network Featuring Flexible Viologen‐Derived Structs

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Three layered cucurbit[6]uril-based metal–organic rotaxane networks functionalized by sulfonic groups for proton conduction

Abstract: Three new cucurbit[6]uril (CB[6])-based metal-organic rotaxane networks (MORNs) (named as CUST-711, CUST-712, CUST-713) functionalized by sulfonic group (-SO3H) have been designed and synthesized via hydrothermal method. All three compounds exhibited...

Cited by 7 publications

References 48 publications

SCSC Transformation and Post-Synthesis Modification of MOFs with Proton Conduction and Ratiometric Fluorescence-Sensing Properties

SCSC Transformation and Post-Synthesis Modification of MOFs with Proton Conduction and Ratiometric Fluorescence-Sensing Properties

Two new transition metal–organic frameworks as multiresponsive fluorescence sensors for detecting Fe3+, Cr2O72− and TNP

Dual Response to Light and Heat of a Metal–Organic Rotaxane Network Featuring Flexible Viologen‐Derived Structs

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Two new transition metal–organic frameworks as multiresponsive fluorescence sensors for detecting Fe³⁺, Cr₂O₇²⁻ and TNP