A Capping‐assisted Strategy for Synthesis of Glass‐like Carboxylate‐based Coordination Polymers

The direct preparation of glass‐like carboxylate‐based coordination polymers (CPs) possessing continuous internal structure and transparency is challenging due to the lack of control on coordination kinetics and subsequently the range of order. Herein, a capping‐assisted strategy was presented to co...

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Published in:Angewandte Chemie International Edition Vol. 64; no. 24; pp. e202500266 - n/a
Main Authors: Albolkany, Mohamed K., Cui, Songlin, Zhao, Yuan, Liu, Bo
Format: Journal Article
Language:English
Published: Germany Wiley Subscription Services, Inc 10.06.2025
Edition:International ed. in English
Subjects:
Amorphous carboxylate MOFs
Benzene
Capping
Capping effect
Cations
Coordination polymers
Copper
Crosslinking
Crystallization
Fine structure
Glass‐like coordination polymers
Ligands
Mechanically robust glassy MOFs
Polymers
Ultrastructure
Wear resistance
Capping effect
Glass‐like coordination polymers
Mechanically robust glassy MOFs
Amorphous carboxylate MOFs
ISSN:1433-7851, 1521-3773, 1521-3773
Online Access:Get full text
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Summary:The direct preparation of glass‐like carboxylate‐based coordination polymers (CPs) possessing continuous internal structure and transparency is challenging due to the lack of control on coordination kinetics and subsequently the range of order. Herein, a capping‐assisted strategy was presented to control the molecular assembly during the metal‐ligand coordination in the solution and to inhibit the long‐range of order hence building glass‐like CPs (g‐CPs) mimicking the polymerization process. 1,3,5‐benzene tricarboxylate (BTC) ligand was used to connect the copper cations (Cu2+) into metal‐organic complexes of different Cu: BTC ratios (metal‐organic pool) in presence of an excess of triethyl amine as a capping agent. Concentrating the Cu‐BTC complexes and further drying under mild conditions induced the decapping process which triggered the random crosslinking between the free carboxylate and Cu2+ to form a boundary‐free continuous internal structure. The as‐prepared Cu‐BTC g‐CP exhibited an approximately similar fine structure like its crystalline counterpart (HKUST‐1), which facilitated solvent and thermal‐induced crystallization. Due to the internal structure continuity, the g‐CP possesses ceramic‐like hardness and wear resistance and plastic‐like resilience. This capping‐assisted strategy has been successfully extended to Ni‐BTC and Fe‐BTC systems under mild conditions and thus presenting a general method for the formation of glass‐like carboxylate‐based CPs. A direct synthesis strategy depending on capping effect was proposed for preparing glass‐like coordination polymers for the first time. The prepared glassy coordination polymers possessed excellent mechanical properties and fraction resistance comparable with ceramics and plastic‐like resilience.
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202500266