Creating glassy states of dicarboxylate-bridged coordination polymers

Fan, Zeyu; Wei, Yong-Sheng; Das, Chinmoy; Kanamori, Kazuyoshi; Yamada, Hiroki; Ohara, Koji; Horike, Satoshi

doi:10.1039/d3cc04518h

Cited by 5 publications

(3 citation statements)

References 42 publications

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“…130 This has also been demonstrated in coordination polymers containing terephthalate linkers. 131 These unprecedented results promise new and exciting avenues to obtain hybrid glasses (Table 4).…”

Section: Non-reversible High Temperature Phase Transitionsmentioning

confidence: 99%

Thermally activated structural phase transitions and processes in metal–organic frameworks

Castillo-Blas,

Chester,

Keen

et al. 2024

Chem. Soc. Rev.

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Section: Non-reversible High Temperature Phase Transitionsmentioning

confidence: 99%

Thermally activated structural phase transitions and processes in metal–organic frameworks

Castillo-Blas,

Chester,

Keen

et al. 2024

Chem. Soc. Rev.

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“…Consequently, the number of known glassy coordinative networks is very limited compared to the vast library of crystalline metalorganic frameworks (MOFs), and even smaller fractions of these networks have gas accessible microporosity. [3][4][5][6][7][8][9][10] Although perturbative and other methods have allowed additional MOFs to be vitri ed, [11][12][13][14] there has been no systematic strategy for synthesizing coordination network glasses with high internal surface areas.…”

Section: Introductionmentioning

confidence: 99%

Transparent and High-porosity Aluminum Alkoxide Network-forming Glasses

Zhao,

Zhang

2024

Preprint

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Metal-organic network-forming glasses are an emerging type of material capable of combining the modular design and high porosity of metal-organic frameworks and the high processability and optical transparency of glasses. However, a generalizable strategy for achieving both high porosity and high glass forming ability in modularly designed metal-organic networks has yet to be developed. Herein, we developed a new series of metal-organic network-forming glasses, aluminum alkoxide glasses, by linking aluminum-oxo clusters with alcohol linkers in the presence of a modulator template. These glasses exhibit well-defined glass transitions and high surface areas up to 500 m2/g, making them one of the most porous glassy materials. The aluminum alkoxide glasses also have optical transparency and fluorescent properties, and their structures were elucidated by pair-distribution functions and compositional analysis. A systematic glass transition study suggested that progressive increase in network connectivity during the evaporation of a coordinatively competitive solvent is key to the bottom-up glass synthesis. Aluminum alkoxide glass can also encapsulate crystalline MOFs to yield composite materials with higher porosities. These findings could significantly expand the library of microporous metal-organic network-forming glasses and enable their future applications.

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“…Considering the vast number of MOFs are metal-carboxylate frameworks, how to melt these technologically important systems with intrinsic moderate decomposition temperatures ( T d , ~200–500 °C) 20 remains a great challenge but is highly sought after 21 . Several carboxylate MOFs, including both carboxylates and bicarboxylates, have been made into glasses very recently, which are derived from discrete solvated complexes or coordination networks through rearrangements of coordination bonds upon desolvation 22 – 24 . Taking advantage of the flexibility and low symmetry of the aliphatic carboxylate ligands and the lack of crystal field stabilization energy on metal ions, a selection of glasses comprising low oxidation state metals (Mg 2+ , Mn 2+ ) and flexible adipate were reported very recently 25 .…”

Section: Introductionmentioning

confidence: 99%

Melt-quenched glass formation of a family of metal-carboxylate frameworks

Xue,

Li,

Chen

et al. 2024

Nat Commun

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Metal-organic framework (MOF) glasses are an emerging class of glasses which complement traditional inorganic, organic and metallic counterparts due to their hybrid nature. Although a few zeolitic imidazolate frameworks have been made into glasses, how to melt and quench the largest subclass of MOFs, metal carboxylate frameworks, into glasses remains challenging. Here, we develop a strategy by grafting the zwitterions on the carboxylate ligands and incorporating organic acids in the framework channels to enable the glass formation. The charge delocalization of zwitterion-acid subsystem and the densely filled channels facilitate the coordination bonding mismatch and thus reduce the melting temperature. Following melt-quenching realizes the glass formation of a family of carboxylate MOFs (UiO-67, UiO-68 and DUT-5), which are usually believed to be un-meltable. Our work opens up an avenue for melt-quenching porous molecular solids into glasses.

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Creating glassy states of dicarboxylate-bridged coordination polymers

Abstract: A series of dicarboxylate-bridged networked glasses with tunable porosity and mechanical properties were obtained by dehydration of hydrated coordination polymer crystals.

Cited by 5 publications

References 42 publications

Thermally activated structural phase transitions and processes in metal–organic frameworks

Thermally activated structural phase transitions and processes in metal–organic frameworks

Transparent and High-porosity Aluminum Alkoxide Network-forming Glasses

Melt-quenched glass formation of a family of metal-carboxylate frameworks

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