Controllable Synthesis and Ultrahigh Anisotropic Single-Crystal Proton Conduction of a Hydrogen-Bonded Organic Framework

Wu, Wenwen; Li, Beibei; Wang, Mengmeng; Cai, Junjie; Andra, Swetha; Lun, Hui-Jie; Bai, Yan; Dang, Dong-Bin; Li, Yamin

doi:10.1021/acs.chemmater.3c01669

Cited by 22 publications

(5 citation statements)

References 47 publications

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“…As shown in Figure b, as the temperature rose from 30 to 75 °C under 80% RH, the conductivity increased continuously to 3.07 × 10 –2 S cm –1 , which was attributed to the acceleration of proton transfer with the temperature rising up (Figure b) . Although ordinary in comparison with the proton-conducting materials such as MOF, COF, HOF, etc., it is superior to typical proton-conducting materials in POMs ,− (Table S7). At last, the activation energy ( E a ) was evaluated by the Arrhenius equation [σ T = σ 0 exp(− E a / k b T )], and calculations showed that E a at 80% RH was estimated to be 0.22 eV (Figure d), indicating that the Grotthuss mechanism is dominant during the process of proton conduction, given that E a is in the range from 0.1 to 0.4 eV .…”

Section: Resultsmentioning

confidence: 99%

Controlled Assembly of a Dawson-like Antimoniotungstate-Supported Trefoil-type Trimer with Good Proton Conductivity Performance

Sun,

Zou,

et al. 2024

Inorg. Chem.

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With the excellent properties of POM in the field of proton conductivity, the preparation of POM-based proton-conductive materials has burst into life. Herein, an unprecedented Sb-templated all-inorganic trimer Na 8 H 18.64 [(SbW 14 O 52 ) 3 (Sb 2 W 6.12 Ru 5.88 O 18 )]•85H 2 O (1), which is based on tetravacant Dawson-like [SbW 14 O 52 ] 17− blocks and exhibits a trefoil type with D 3 symmetry, has been successfully designed and synthesized by the assembly of simple materials with a one-pot hydrothermal method under acidic conditions. Also, compound 1 is systematically characterized by singlecrystal X-ray diffraction, PXRD, ESI-MS, IR spectroscopy, UV−vis, elemental analysis, and TGA. Crystal structure data analysis demonstrates that compound 1 is constructed by a hexagonal prismatic heterometallic {Sb 2 W 6.12 Ru 5.88 O 18 } core and three equivalent {SbW 14 } units bridged through μ 2 -O atoms in periphery. Subsequently, further property experiments show that compound 1 exhibits high proton conductivity with a conductivity value (σ) of 3.07 × 10 −2 S cm −1 at 75 °C and 80% relative humidity (RH). The activation energy of compound 1 evaluated by the Arrhenius plots is 0.22 eV, which indicates that the Grotthuss mechanism is dominant during the process of proton transfer.

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Section: Resultsmentioning

confidence: 99%

Controlled Assembly of a Dawson-like Antimoniotungstate-Supported Trefoil-type Trimer with Good Proton Conductivity Performance

Sun,

Zou,

et al. 2024

Inorg. Chem.

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“…[153] Lun et al constructed four three-dimensional HOFs (GC-1, À 2, À 3, and À 4) with 1, 2, 4, 5benzenetetracarboxylic acid and guanidine and its derivatives, in which GC-1 undergoes a water-induced SCSC transformation to the more stable GC-2 with continuous π-π stacking (Figure 11b). [167] Notably, the GC-2 single-crystal samples are highly anisotropic, with a proton conductivity of 1.78×10 À 2 S cm À 1 along the [100] direction at ambient temperature and 98 % RH, which is 3-5 orders of magnitude higher than that along the [010] and [001] directions. This is associated with the formation of a continuous hydrogen bonding network and hydrophilic channel formation between the guanidine cation and the carboxylic acid anion along the a-axis direction.…”

Section: Proton Conductionmentioning

confidence: 99%

Charge‐Assisted Ionic Hydrogen‐Bonded Organic Frameworks: Designable and Stabilized Multifunctional Materials

Chen,

Cao,

Bai

et al. 2024

Chemistry A European J

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Hydrogen‐bonded organic frameworks (HOFs) are a class of crystalline framework materials assembled by hydrogen bonds. HOFs have the advantages of high crystallinity, mild reaction conditions, good solution processability, and reproducibility. Coupled with the reversibility and flexibility of hydrogen bonds, HOFs can be assembled into a wide diversity of crystalline structures. Since the bonding energy of hydrogen bonds is lower than that of ligand and covalent bonds, the framework of HOFs is prone to collapse after desolventisation and the stability is not high, which limits the development and application of HOFs. In recent years, numerous stable and functional HOFs have been developed by π‐π stacking, highly interpenetrated networks, charge‐assisted, ligand‐bond‐assisted, molecular weaving, and covalent cross‐linking. Charge‐assisted ionic HOFs introduce electrostatic attraction into HOFs to improve stability while enriching structural diversity and functionality. In this paper, we review the development, the principles of rational design and assembly of charge‐assisted ionic HOFs, introduces the different building block construction modes of charge‐assisted ionic HOFs. Highlight the applications of charge‐assisted ionic HOFs in gas adsorption and separation, proton conduction, biological applications, etc., and prospects for the diverse design of charge‐assisted ionic HOFs structures and multifunctional applications.

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“…With some modifications to the initially reported method, GC-2 was prepared. 57 The specific synthetic operations are detailed in the Supporting Information.…”

Section: ■ Introductionmentioning

confidence: 99%

Efficient Multi-stimulus-Responsive Luminescent Eu(III)-Modified HOFs Materials: Detecting Thiram and Caffeic Acid and Constructing a Flexible Substrate Anti-counterfeiting Platform

Yang,

Zhu,

Yan

2024

ACS Appl. Mater. Interfaces

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The powerful capability of multi-stimulus-responsive luminescent hydrogen-bonded organic frameworks (HOFs) to respond to external chemical or physical stimuli in various manners makes them appealing in the luminescence anti-counterfeiting field. Herein, a novel Eu 3+ -functionalized HOF (Eu@GC-2) that combines the emission of HOFs with the characteristic emission of Eu 3+ ions has been successfully synthesized, which can generate various fluorescence at different excitation wavelengths. Eu@GC-2 has enormous potential as a raw material for a paper-based sensor that is designed for detecting the pesticides thiram and caffeic acid in crops with favorable selectivity, anti-interference, and high efficiency. Based on the above excellent properties, Ln 3+ -functionalized HOFs (Ln@GC-2) were then employed to produce four luminescent anti-counterfeiting inks. With the incorporation of back-propagation neural network and Gray code conversion functions, a multi-stimulus-responsive luminescent anti-counterfeiting platform, coregulated by the excitation light and the chemical reagent, has been constructed. This approach can not only achieve multiple encryptions and fast information identification but also enhance the code-breaking complexity, making it an efficient strategy for information encryption and decryption.

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Controllable Synthesis and Ultrahigh Anisotropic Single-Crystal Proton Conduction of a Hydrogen-Bonded Organic Framework

Cited by 22 publications

References 47 publications

Controlled Assembly of a Dawson-like Antimoniotungstate-Supported Trefoil-type Trimer with Good Proton Conductivity Performance

Controlled Assembly of a Dawson-like Antimoniotungstate-Supported Trefoil-type Trimer with Good Proton Conductivity Performance

Charge‐Assisted Ionic Hydrogen‐Bonded Organic Frameworks: Designable and Stabilized Multifunctional Materials

Efficient Multi-stimulus-Responsive Luminescent Eu(III)-Modified HOFs Materials: Detecting Thiram and Caffeic Acid and Constructing a Flexible Substrate Anti-counterfeiting Platform

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