Zero- to One-Dimensional Transformation in a Highly Porous Metal-Organic Framework to Enhance Physicochemical Properties

Enhui Jiang; Daisong Chen; Zhuoliang Ying; Jiaming Zhou; Artit Jarusarunchai; Xinyu Zhang; Chenxi Xiong; Keunhong Jeong; Dong-Myeong Shin; Jin Shang; Seungkyu Lee

doi:10.1021/jacs.5c03967

Zero- to One-Dimensional Transformation in a Highly Porous Metal-Organic Framework to Enhance Physicochemical Properties

Enhui Jiang (Co-first Author), Daisong Chen (Co-first Author), Zhuoliang Ying, Jiaming Zhou, Artit Jarusarunchai, Xinyu Zhang, Chenxi Xiong, Keunhong Jeong, Dong-Myeong Shin, Jin Shang^*, Seungkyu Lee^*

^*Corresponding author for this work

School of Energy and Environment

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

2 Citations (Scopus)

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Abstract

The dynamic behaviors of metal-organic frameworks (MOFs) continue to expand the accessible architectures and properties within this material class. However, the dynamic behaviors that can be studied in MOFs are limited to the transitions, preserving their high crystallinity. For this reason, their significant structural changes involving coordination bond breakage and rearrangement remain largely underexplored. Herein, we report a three-step single-crystal-to-single-crystal (SCSC) phase transition in a new cerium-based MOF, HKU-9 [Ce₂PET(DMF)₂(H₂O)₂], transforming zero-dimensional (0D) secondary building units (SBUs) into one-dimensional (1D) chain SBUs in HKU-90 [Ce₂(μ-H₂O)PET(H₂O)₂]. Single-crystal X-ray diffraction studies unambiguously delineate the structural evolution at each stage of this multistep transition, revealing multiple coordination bond dissociations/associations and a significant lattice contraction─all while preserving single-crystal integrity. This dimensional transformation endows HKU-90 with enhanced chemical stability (pH 1-10) and a record-high Brunauer-Emmett-Teller (BET) surface area of 2660 m² g^-1 among reported Ce-based MOFs. Further, HKU-90 exhibits exceptional gas sorption performance, with one of the highest reported C₂H₂ storage capacities (184 cc g^-1 at 273 K, 1 bar) and outstanding C₂H₂/CO₂ selectivity (2.16) under these conditions. Notably, the formation of 1D chain SBUs, a structural motif found in many high-performance MOFs, highlights the potential of using the solid-state fusion of multinuclear metal clusters to tailor the properties of the framework. © 2025 The Authors. Published by American Chemical Society.

Original language	English
Pages (from-to)	16766–16772
Journal	Journal of the American Chemical Society
Volume	147
Issue number	20
Online published	7 May 2025
DOIs	https://doi.org/10.1021/jacs.5c03967
Publication status	Published - 21 May 2025

Funding

We gratefully acknowledge financial support from the Research Grants Council of Hong Kong under the Early Career Scheme (No. 27308123), General Research Fund (No. 17201721), and Project Ref. CityU 11310223. We also thank the staff at the Shanghai Synchrotron Radiation Facility (SSRF, China) for their assistance at BL17B1 and BL03HB (Project Nos. 2023-NFPS-PT-500591, 2024-NFPS-PT-500979, 2024-SSRF-HZ-505601).

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title = "Zero- to One-Dimensional Transformation in a Highly Porous Metal-Organic Framework to Enhance Physicochemical Properties",

abstract = "The dynamic behaviors of metal-organic frameworks (MOFs) continue to expand the accessible architectures and properties within this material class. However, the dynamic behaviors that can be studied in MOFs are limited to the transitions, preserving their high crystallinity. For this reason, their significant structural changes involving coordination bond breakage and rearrangement remain largely underexplored. Herein, we report a three-step single-crystal-to-single-crystal (SCSC) phase transition in a new cerium-based MOF, HKU-9 [Ce2PET(DMF)2(H2O)2], transforming zero-dimensional (0D) secondary building units (SBUs) into one-dimensional (1D) chain SBUs in HKU-90 [Ce2(μ-H2O)PET(H2O)2]. Single-crystal X-ray diffraction studies unambiguously delineate the structural evolution at each stage of this multistep transition, revealing multiple coordination bond dissociations/associations and a significant lattice contraction─all while preserving single-crystal integrity. This dimensional transformation endows HKU-90 with enhanced chemical stability (pH 1-10) and a record-high Brunauer-Emmett-Teller (BET) surface area of 2660 m2 g-1 among reported Ce-based MOFs. Further, HKU-90 exhibits exceptional gas sorption performance, with one of the highest reported C2H2 storage capacities (184 cc g-1 at 273 K, 1 bar) and outstanding C2H2/CO2 selectivity (2.16) under these conditions. Notably, the formation of 1D chain SBUs, a structural motif found in many high-performance MOFs, highlights the potential of using the solid-state fusion of multinuclear metal clusters to tailor the properties of the framework. {\textcopyright} 2025 The Authors. Published by American Chemical Society.",

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Zero- to One-Dimensional Transformation in a Highly Porous Metal-Organic Framework to Enhance Physicochemical Properties. / Jiang, Enhui (Co-first Author); Chen, Daisong (Co-first Author); Ying, Zhuoliang et al.
In: Journal of the American Chemical Society, Vol. 147, No. 20, 21.05.2025, p. 16766–16772.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Zero- to One-Dimensional Transformation in a Highly Porous Metal-Organic Framework to Enhance Physicochemical Properties

AU - Jiang, Enhui

AU - Chen, Daisong

AU - Ying, Zhuoliang

AU - Zhou, Jiaming

AU - Jarusarunchai, Artit

AU - Zhang, Xinyu

AU - Xiong, Chenxi

AU - Jeong, Keunhong

AU - Shin, Dong-Myeong

AU - Shang, Jin

AU - Lee, Seungkyu

PY - 2025/5/21

Y1 - 2025/5/21

N2 - The dynamic behaviors of metal-organic frameworks (MOFs) continue to expand the accessible architectures and properties within this material class. However, the dynamic behaviors that can be studied in MOFs are limited to the transitions, preserving their high crystallinity. For this reason, their significant structural changes involving coordination bond breakage and rearrangement remain largely underexplored. Herein, we report a three-step single-crystal-to-single-crystal (SCSC) phase transition in a new cerium-based MOF, HKU-9 [Ce2PET(DMF)2(H2O)2], transforming zero-dimensional (0D) secondary building units (SBUs) into one-dimensional (1D) chain SBUs in HKU-90 [Ce2(μ-H2O)PET(H2O)2]. Single-crystal X-ray diffraction studies unambiguously delineate the structural evolution at each stage of this multistep transition, revealing multiple coordination bond dissociations/associations and a significant lattice contraction─all while preserving single-crystal integrity. This dimensional transformation endows HKU-90 with enhanced chemical stability (pH 1-10) and a record-high Brunauer-Emmett-Teller (BET) surface area of 2660 m2 g-1 among reported Ce-based MOFs. Further, HKU-90 exhibits exceptional gas sorption performance, with one of the highest reported C2H2 storage capacities (184 cc g-1 at 273 K, 1 bar) and outstanding C2H2/CO2 selectivity (2.16) under these conditions. Notably, the formation of 1D chain SBUs, a structural motif found in many high-performance MOFs, highlights the potential of using the solid-state fusion of multinuclear metal clusters to tailor the properties of the framework. © 2025 The Authors. Published by American Chemical Society.

AB - The dynamic behaviors of metal-organic frameworks (MOFs) continue to expand the accessible architectures and properties within this material class. However, the dynamic behaviors that can be studied in MOFs are limited to the transitions, preserving their high crystallinity. For this reason, their significant structural changes involving coordination bond breakage and rearrangement remain largely underexplored. Herein, we report a three-step single-crystal-to-single-crystal (SCSC) phase transition in a new cerium-based MOF, HKU-9 [Ce2PET(DMF)2(H2O)2], transforming zero-dimensional (0D) secondary building units (SBUs) into one-dimensional (1D) chain SBUs in HKU-90 [Ce2(μ-H2O)PET(H2O)2]. Single-crystal X-ray diffraction studies unambiguously delineate the structural evolution at each stage of this multistep transition, revealing multiple coordination bond dissociations/associations and a significant lattice contraction─all while preserving single-crystal integrity. This dimensional transformation endows HKU-90 with enhanced chemical stability (pH 1-10) and a record-high Brunauer-Emmett-Teller (BET) surface area of 2660 m2 g-1 among reported Ce-based MOFs. Further, HKU-90 exhibits exceptional gas sorption performance, with one of the highest reported C2H2 storage capacities (184 cc g-1 at 273 K, 1 bar) and outstanding C2H2/CO2 selectivity (2.16) under these conditions. Notably, the formation of 1D chain SBUs, a structural motif found in many high-performance MOFs, highlights the potential of using the solid-state fusion of multinuclear metal clusters to tailor the properties of the framework. © 2025 The Authors. Published by American Chemical Society.

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Zero- to One-Dimensional Transformation in a Highly Porous Metal-Organic Framework to Enhance Physicochemical Properties

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GRF: Selective Gas Adsorption by Single-atom Extraframework Transition Metal Sites Regularly Arranged Inside Porous Crystalline Matrices

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Zero- to One-Dimensional Transformation in a Highly Porous Metal-Organic Framework to Enhance Physicochemical Properties

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GRF: Selective Gas Adsorption by Single-atom Extraframework Transition Metal Sites Regularly Arranged Inside Porous Crystalline Matrices

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