Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs

Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng; Lu, Weigang; Zou, Lanfang; Zhang, Qiang; Wang, Xuan; Sun, Xing; Zhou, Hong-Cai

doi:10.1021/jacs.6b04501

Title: Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs

Journal Article · Sat Jun 25 00:00:00 EDT 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b04501· OSTI ID:1388673

Yuan, Shuai ^[1]; Chen, Ying-Pin ^[1]; Qin, Jun-Sheng ^[1]; Lu, Weigang ^[2]; Zou, Lanfang ^[1]; Zhang, Qiang ^[1]; Wang, Xuan ^[1]; Sun, Xing ^[1]; Zhou, Hong-Cai ^[1]

Texas A & M Univ., College Station, TX (United States)
Blinn College, Bryan, TX (United States)

Precise placement of multiple functional groups in a highly ordered metal–organic framework (MOF) platform allows the tailoring of the pore environment, which is required for advanced applications. To realize this, we present a comprehensive study on the linker installation method, in which a stable MOF with coordinatively unsaturated Zr₆ clusters was employed and linkers bearing different functional groups were postsynthetically installed. Specifically, a Zr-MOF with inherent missing linker sites, namely, PCN-700, was initially constructed under kinetic control. Twelve linkers with different substituents were then designed to study their effect on MOF formation kinetics and therefore resulting MOF structures. Guided by the geometrical analysis, linkers with different lengths were installed into a parent PCN-700, giving rise to 11 new MOFs and each bearing up to three different functional groups in predefined positions. Systematic variation of the pore volume and decoration of pore environment were realized by linker installation, which resulted in synergistic effects including an enhancement of H2 adsorption capacities of up to 57%. In addition, a size-selective catalytic system for aerobic alcohol oxidation reaction is built in PCN-700 through linker installation, which shows high activity and tunable size selectivity. Altogether, these results exemplify the capability of the linker installation method in the pore environment engineering of stable MOFs with multiple functional groups, giving an unparalleled level of control.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001015; EE0007049

OSTI ID:: 1388673

Journal Information:: Journal of the American Chemical Society, Vol. 138, Issue 28; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 207 works

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Selective adsorption of chlorinated volatile organic compound vapours by microcrystalline 1D coordination polymers Cametti, Massimo; Martí-Rujas, Javier Dalton Transactions, Vol. 45, Issue 47 https://doi.org/10.1039/c6dt03803d	journal	January 2016
A Robust Metal-Organic Framework Combining Open Metal Sites and Polar Groups for Methane Purification and CO ₂ /Fluorocarbon Capture Chen, Cheng-Xia; Zheng, Shao-Ping; Wei, Zhang-Wen Chemistry - A European Journal, Vol. 23, Issue 17 https://doi.org/10.1002/chem.201606038	journal	March 2017
Retrosynthesis of multi-component metal−organic frameworks Yuan, Shuai; Qin, Jun-Sheng; Li, Jialuo Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03102-5	journal	February 2018
One-pot synthesis of mercapto functionalized Zr-MOFs for the enhanced removal of Hg ²⁺ ions from water Lin, Daiwu; Liu, Xiao; Huang, Renliang Chemical Communications, Vol. 55, Issue 47 https://doi.org/10.1039/c9cc03481a	journal	January 2019
Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks Bitzer, Johannes; Kleist, Wolfgang Chemistry – A European Journal, Vol. 25, Issue 8 https://doi.org/10.1002/chem.201803887	journal	January 2019
Stepwise engineering of pore environments and enhancement of CO ₂ /R22 adsorption capacity through dynamic spacer installation and functionality modification Chen, Cheng-Xia; Qiu, Qian-Feng; Cao, Chen-Chen Chem. Commun., Vol. 53, Issue 83 https://doi.org/10.1039/c7cc06352k	journal	January 2017
Why Design Matters: From Decorated Metal Oxide Clusters to Functional Metal–Organic Frameworks Schoedel, Alexander; Rajeh, Sahar Topics in Current Chemistry, Vol. 378, Issue 1 https://doi.org/10.1007/s41061-020-0281-0	journal	February 2020
Harnessing Bottom‐Up Self‐Assembly To Position Five Distinct Components in an Ordered Porous Framework Tu, Binbin; Diestel, Lisa; Shi, Zhao‐Lin Angewandte Chemie, Vol. 131, Issue 16 https://doi.org/10.1002/ange.201900863	journal	February 2019
Investigating the crystal engineering of the pillared paddlewheel metal–organic framework Zn ₂ (NH ₂ BDC) ₂ DABCO McGrath, D. T.; Downing, V. A.; Katz, M. J. CrystEngComm, Vol. 20, Issue 39 https://doi.org/10.1039/c8ce00848e	journal	January 2018
Improving analyte selectivity by post-assembly modification of metal–organic framework based photonic crystal sensors von Mankowski, A.; Szendrei-Temesi, K.; Koschnick, C. Nanoscale Horizons, Vol. 3, Issue 4 https://doi.org/10.1039/c7nh00209b	journal	January 2018
Made-to-order porous electrodes for supercapacitors: MOFs embedded with redox-active centers as a case study Mallick, Arijit; Liang, Hanfeng; Shekhah, Osama Chemical Communications, Vol. 56, Issue 12 https://doi.org/10.1039/c9cc08860a	journal	January 2020
Dynamic Covalent Chemistry within Biphenyl Scaffolds: Reversible Covalent Bonding, Control of Selectivity, and Chirality Sensing with a Single System Ni, Cailing; Zha, Daijun; Ye, Hebo Angewandte Chemie, Vol. 130, Issue 5 https://doi.org/10.1002/ange.201711602	journal	January 2018
Flexible Zirconium MOFs as Bromine-Nanocontainers for Bromination Reactions under Ambient Conditions Pang, Jiandong; Yuan, Shuai; Du, Dongying Angewandte Chemie, Vol. 129, Issue 46 https://doi.org/10.1002/ange.201709186	journal	October 2017
Evans–Showell-type polyoxometalate-based metal–organic complexes with novel 3D structures constructed from flexible bis-pyrazine–bis-amide ligands and copper metals: syntheses, structures, and fluorescence and catalytic properties Li, Feng-Cai; Li, Xi-Li; Tan, Li-Kun Dalton Transactions, Vol. 48, Issue 6 https://doi.org/10.1039/c8dt04698k	journal	January 2019
Technology for the Remediation of Water Pollution: A Review on the Fabrication of Metal Organic Frameworks Bian, Yongning; Xiong, Nana; Zhu, Guocheng Processes, Vol. 6, Issue 8 https://doi.org/10.3390/pr6080122	journal	August 2018
Uniform and simultaneous orthogonal functionalization of a metal–organic framework material Samarakoon, Kanchana P.; Yazdanparast, Mohammad S.; Day, Victor W. Molecular Systems Design & Engineering, Vol. 5, Issue 4 https://doi.org/10.1039/c9me00182d	journal	January 2020
A 2D porous pentiptycene-based MOF for efficient detection of Ba ²⁺ and selective adsorption of dyes from water Zhang, Minghui; Qi, Ziqiang; Feng, Yang Inorganic Chemistry Frontiers, Vol. 5, Issue 6 https://doi.org/10.1039/c8qi00098k	journal	January 2018
Symmetry-guided syntheses of mixed-linker Zr metal–organic frameworks with precise linker locations Kim, Hyehyun; Kim, Dongwook; Moon, Dohyun Chemical Science, Vol. 10, Issue 22 https://doi.org/10.1039/c9sc01301f	journal	January 2019
A terbium( iii ) lanthanide–organic framework as a platform for a recyclable multi-responsive luminescent sensor Chen, Min; Xu, Wen-Ming; Tian, Jia-Yue Journal of Materials Chemistry C, Vol. 5, Issue 8 https://doi.org/10.1039/c6tc05615f	journal	January 2017
Four new metal–organic frameworks based on diverse secondary building units: sensing and magnetic properties Yan, Yang-Tian; Zhang, Wen-Yan; Zhang, Fang Dalton Transactions, Vol. 47, Issue 5 https://doi.org/10.1039/c7dt04696k	journal	January 2018
A fast and highly selective Congo red adsorption material based on a cadmium-phosphonate network Ai, Jing; Tian, Hong-Rui; Min, Xue Dalton Transactions https://doi.org/10.1039/c9dt01545k	journal	January 2020
A robust two-dimensional zirconium-based luminescent coordination polymer built on a V-shaped dicarboxylate ligand for vapor phase sensing of volatile organic compounds Du, Pei-Yao; Lustig, William P.; Teat, Simon J. Chemical Communications, Vol. 54, Issue 58 https://doi.org/10.1039/c8cc03496f	journal	January 2018
Mixed-linker strategy for the construction of multifunctional metal–organic frameworks Qin, Jun-Sheng; Yuan, Shuai; Wang, Qi Journal of Materials Chemistry A, Vol. 5, Issue 9 https://doi.org/10.1039/c6ta10281f	journal	January 2017
Retrofitting metal-organic frameworks Schneider, Christian; Bodesheim, David; Keupp, Julian Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12876-1	journal	October 2019
A flexible thioether-based MOF as a crystalline sponge for structural characterization of liquid organic molecules Yang, Xin-Yu; Yuan, Shuai; Qin, Jun-Sheng Materials Chemistry Frontiers, Vol. 1, Issue 9 https://doi.org/10.1039/c7qm00152e	journal	January 2017
Harnessing Bottom-Up Self-Assembly To Position Five Distinct Components in an Ordered Porous Framework Tu, Binbin; Diestel, Lisa; Shi, Zhao-Lin Angewandte Chemie International Edition, Vol. 58, Issue 16 https://doi.org/10.1002/anie.201900863	journal	March 2019
Encapsulation of Crabtree's Catalyst in Sulfonated MIL-101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment Grigoropoulos, Alexios; McKay, Alasdair I.; Katsoulidis, Alexandros P. Angewandte Chemie, Vol. 130, Issue 17 https://doi.org/10.1002/ange.201710091	journal	March 2018
Pore-Environment Engineering with Multiple Metal Sites in Rare-Earth Porphyrinic Metal-Organic Frameworks Zhang, Liangliang; Yuan, Shuai; Feng, Liang Angewandte Chemie International Edition, Vol. 57, Issue 18 https://doi.org/10.1002/anie.201802661	journal	March 2018
Dynamic Covalent Chemistry within Biphenyl Scaffolds: Reversible Covalent Bonding, Control of Selectivity, and Chirality Sensing with a Single System Ni, Cailing; Zha, Daijun; Ye, Hebo Angewandte Chemie International Edition, Vol. 57, Issue 5 https://doi.org/10.1002/anie.201711602	journal	January 2018
Molecular Vise Approach to Create Metal-Binding Sites in MOFs and Detection of Biomarkers Wang, Yang; Liu, Qi; Zhang, Qin Angewandte Chemie International Edition, Vol. 57, Issue 24 https://doi.org/10.1002/anie.201803201	journal	May 2018
Flexible Zirconium MOFs as Bromine-Nanocontainers for Bromination Reactions under Ambient Conditions Pang, Jiandong; Yuan, Shuai; Du, Dongying Angewandte Chemie International Edition, Vol. 56, Issue 46 https://doi.org/10.1002/anie.201709186	journal	October 2017
Stable Metal–Organic Frameworks with Group 4 Metals: Current Status and Trends Yuan, Shuai; Qin, Jun-Sheng; Lollar, Christina T. ACS Central Science, Vol. 4, Issue 4 https://doi.org/10.1021/acscentsci.8b00073	journal	February 2018
Uncovering Two Principles of Multivariate Hierarchical Metal–Organic Framework Synthesis via Retrosynthetic Design Feng, Liang; Yuan, Shuai; Li, Jia-Luo ACS Central Science, Vol. 4, Issue 12 https://doi.org/10.1021/acscentsci.8b00722	journal	December 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
membrane
carbon capture
materials and chemistry by design
synthesis (novel materials)
synthesis (self-assembly)
synthesis (scalable processing)
alcohols
metal organic frameworks
substituents
chemical structure
functional groups

CCDC 1496844: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7l9r The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496840: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7l5m The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496831: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7kw9 The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496828: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7ks6 The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496833: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7kyc The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496845: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7lbs The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496835: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7l0g The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496843: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7l8q The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496830: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7kv8 The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496827: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7kr5 The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496832: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7kxb The current record is supplemented by this dataset	dataset	January 2016
CCDC 1036874: Experimental Crystal Structure Determination Yuan, Shuai; Lu, Weigang; Chen, Ying-Pin https://doi.org/10.5517/cc13sykd The current record is supplemented by this dataset	dataset	January 2015
CCDC 1496842: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7l7p The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496838: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7l3k The current record is supplemented by this dataset	dataset	January 2016
CCDC 1496837: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7l2j The current record is supplemented by this dataset	dataset	January 2016
CCDC 1036875: Experimental Crystal Structure Determination Yuan, Shuai; Lu, Weigang; Chen, Ying-Pin https://doi.org/10.5517/cc13sylf The current record is supplemented by this dataset	dataset	January 2015
CCDC 1496834: Experimental Crystal Structure Determination Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng https://doi.org/10.5517/ccdc.csd.cc1m7kzd The current record is supplemented by this dataset	dataset	January 2016