Simultaneous Control of Pore-Space Partition and Charge Distribution in Multi-Modular Metal–Organic Frameworks

Hong, Anh N.; Kusumoputro, Emily; Wang, Yanxiang; Yang, Huajun; Chen, Yichong; Bu, Xianhui; Feng, Pingyun

doi:10.1002/anie.202116064

Title: Simultaneous Control of Pore-Space Partition and Charge Distribution in Multi-Modular Metal–Organic Frameworks

Journal Article · 29 January 2022 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202116064 · OSTI ID:1976276

Hong, Anh N. ^[1]; Kusumoputro, Emily ^[2]; Wang, Yanxiang ^[2]; Yang, Huajun ^[3]; Chen, Yichong ^[2];

^[3];

^[2]

University of California, Riverside, CA (United States); OSTI
University of California, Riverside, CA (United States)
California State University (CalState), Long Beach, CA (United States)

Here we report here a strategy for making anionic pacs type porous materials by combining pore space partition with charge reallocation. The method uses the first negatively charged pore partition ligand (2,5,8-tri-(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene, H-tph) that simultaneously enables pore partition and charge reallocation. Over two dozen anionic pacs materials have been made to demonstrate their excellent chemical stability and a high degree of tunability. Notably, Ni₃-bdt-tph (bdt=1,4-benzeneditetrazolate) exhibits month-long water stability, while CoV-bdt-tph sets a new benchmark for C₂H₂ storage capacity under ambient conditions for ionic MOFs. In addition to tunable in-framework modules, we show feasibility to tune the type and concentration of extra-framework counter cations and their influence on both stability and capability to separate industrial C₃H₈/C₃H₆ and C₆H₆/C₆H₁₂ mixtures.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: University of California, Riverside, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: SC0010596

OSTI ID:: 1976276

Alternate ID(s):: OSTI ID: 1844800; OSTI ID: 2205464

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 13 Vol. 61; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Zinc-Adeninate Metal−Organic Framework for Aqueous Encapsulation and Sensitization of Near-infrared and Visible Emitting Lanthanide Cations An, Jihyun; Shade, Chad M.; Chengelis-Czegan, Demetra A. Journal of the American Chemical Society, Vol. 133, Issue 5 https://doi.org/10.1021/ja109103t	journal	February 2011
Multivariable Modular Design of Pore Space Partition Zhao, Xiang; Bu, Xianhui; Nguyen, Edward T. Journal of the American Chemical Society, Vol. 138, Issue 46 https://doi.org/10.1021/jacs.6b07901	journal	November 2016
Cage‐Like Porous Materials with Simultaneous High C ₂ H ₂ Storage and Excellent C ₂ H ₂ /CO ₂ Separation Performance Di, Zhengyi; Liu, Caiping; Pang, Jiandong Angewandte Chemie International Edition, Vol. 60, Issue 19 https://doi.org/10.1002/anie.202101907	journal	March 2021
Cation-Dependent Nonlinear Optical Behavior in an Octupolar 3D Anionic Metal–Organic Open Framework Liu, Yan; Li, Gao; Li, Xing Angewandte Chemie, Vol. 119, Issue 33 https://doi.org/10.1002/ange.200701056	journal	August 2007
Defective Hierarchical Pore Engineering of a Zn–Ni MOF by Labile Coordination Bonding Modulation Ding, Hao-Jing; Zhang, Ying; Wang, Xi Inorganic Chemistry, Vol. 60, Issue 7 https://doi.org/10.1021/acs.inorgchem.1c00164	journal	March 2021
Multiroute Synthesis of Porous Anionic Frameworks and Size-Tunable Extraframework Organic Cation-Controlled Gas Sorption Properties Chen, Shumei; Zhang, Jian; Wu, Tao Journal of the American Chemical Society, Vol. 131, Issue 44 https://doi.org/10.1021/ja906302t	journal	November 2009
A Strategy for Constructing Pore‐Space‐Partitioned MOFs with High Uptake Capacity for C ₂ Hydrocarbons and CO ₂ Wang, Yong; Jia, Xiaoxia; Yang, Huajun Angewandte Chemie International Edition, Vol. 59, Issue 43 https://doi.org/10.1002/anie.202008696	journal	August 2020
Design Strategy for the Controlled Generation of Cationic Frameworks and Ensuing Anion-Exchange Capabilities Brunet, Gabriel; Robeyns, Koen; Huynh, Racheal P. S. ACS Applied Materials & Interfaces, Vol. 11, Issue 3 https://doi.org/10.1021/acsami.8b15946	journal	December 2018
Cage‐Like Porous Materials with Simultaneous High C ₂ H ₂ Storage and Excellent C ₂ H ₂ /CO ₂ Separation Performance Di, Zhengyi; Liu, Caiping; Pang, Jiandong Angewandte Chemie, Vol. 133, Issue 19 https://doi.org/10.1002/ange.202101907	journal	March 2021
Proton Conductivity Control by Ion Substitution in a Highly Proton-Conductive Metal–Organic Framework Sadakiyo, Masaaki; Yamada, Teppei; Kitagawa, Hiroshi Journal of the American Chemical Society, Vol. 136, Issue 38 https://doi.org/10.1021/ja507634v	journal	September 2014
Ethene/Ethane and Propene/Propane Separation via the Olefin and Paraffin Selective Metal–Organic Framework Adsorbents CPO-27 and ZIF-8 Böhme, Ulrike; Barth, Benjamin; Paula, Carolin Langmuir, Vol. 29, Issue 27 https://doi.org/10.1021/la401471g	journal	June 2013
Selective Metal Cation Capture by Soft Anionic Metal–Organic Frameworks via Drastic Single-Crystal-to-Single-Crystal Transformations Tian, Jian; Saraf, Laxmikant V.; Schwenzer, Birgit Journal of the American Chemical Society, Vol. 134, Issue 23 https://doi.org/10.1021/ja303092m	journal	May 2012
Design strategies and applications of charged metal organic frameworks Zhao, Shu-Na; Zhang, Yang; Song, Shu-Yan Coordination Chemistry Reviews, Vol. 398 https://doi.org/10.1016/j.ccr.2019.07.004	journal	November 2019
Cation-induced kinetic trapping and enhanced hydrogen adsorption in a modulated anionic metal–organic framework Yang, Sihai; Lin, Xiang; Blake, Alexander J. Nature Chemistry, Vol. 1, Issue 6 https://doi.org/10.1038/nchem.333	journal	August 2009
Polycatenated Molecular Cage-Based Propane Trap for Propylene Purification with Recorded Selectivity Yang, Lifeng; Cui, Xili; Ding, Qi ACS Applied Materials & Interfaces, Vol. 12, Issue 2 https://doi.org/10.1021/acsami.9b19438	journal	December 2019
Azobenzene Decorated NbO-Type Metal–Organic Framework for High-Capacity Storage of Energy Gases Huang, Pan; Chen, Cheng; Hong, Zixiao Inorganic Chemistry, Vol. 58, Issue 18 https://doi.org/10.1021/acs.inorgchem.9b01205	journal	July 2019
Coordination templated [2+2+2] cyclotrimerization in a porous coordination framework Wei, Yong-Sheng; Zhang, Mei; Liao, Pei-Qin Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9348	journal	September 2015
A pacs-type metal-organic framework based on [Cd3(OH)] clusters for effective C2H2/CO2 separation and ﬂuorescent detection of TNP in water Yang, Hao-Ran; Chen, Wei-Ya; Chen, Di-Ming Journal of Solid State Chemistry, Vol. 291 https://doi.org/10.1016/j.jssc.2020.121658	journal	November 2020
A porous metal-organic framework with ultrahigh acetylene uptake capacity under ambient conditions Pang, Jiandong; Jiang, Feilong; Wu, Mingyan Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8575	journal	June 2015
A Multifunctional Tb-MOF for Highly Discriminative Sensing of Eu ³⁺ /Dy ³⁺ and as a Catalyst Support of Ag Nanoparticles Xu, Guo-Wang; Wu, Ya-Pan; Dong, Wen-Wen Small, Vol. 13, Issue 22 https://doi.org/10.1002/smll.201602996	journal	April 2017
Tunable Rare-Earth fcu-MOFs: A Platform for Systematic Enhancement of CO₂ Adsorption Energetics and Uptake Xue, Dong-Xu; Cairns, Amy J.; Belmabkhout, Youssef Journal of the American Chemical Society, Vol. 135, Issue 20, p. 7660-7667 https://doi.org/10.1021/ja401429x	journal	May 2013
Design and Synthesis of a Water-Stable Anionic Uranium-Based Metal-Organic Framework (MOF) with Ultra Large Pores Li, Peng; Vermeulen, Nicolaas A.; Gong, Xirui Angewandte Chemie International Edition, Vol. 55, Issue 35 https://doi.org/10.1002/anie.201605547	journal	July 2016
Pore-Space Partition and Optimization for Propane-Selective High-Performance Propane/Propylene Separation Hong, Anh N.; Yang, Huajun; Li, Tong ACS Applied Materials & Interfaces, Vol. 13, Issue 44 https://doi.org/10.1021/acsami.1c10391	journal	July 2021
Sulfonic Groups Lined along Channels of Metal–Organic Frameworks (MOFs) for Super-Proton Conductor Liu, Shan-Shan; Han, Zhen; Yang, Jin-Sen Inorganic Chemistry, Vol. 59, Issue 1 https://doi.org/10.1021/acs.inorgchem.9b02649	journal	December 2019
A Strategy for Constructing Pore‐Space‐Partitioned MOFs with High Uptake Capacity for C ₂ Hydrocarbons and CO ₂ Wang, Yong; Jia, Xiaoxia; Yang, Huajun Angewandte Chemie, Vol. 132, Issue 43 https://doi.org/10.1002/ange.202008696	journal	August 2020
Hydrolytic stability in hemilabile metal–organic frameworks McHugh, Lauren N.; McPherson, Matthew J.; McCormick, Laura J. Nature Chemistry, Vol. 10, Issue 11 https://doi.org/10.1038/s41557-018-0104-x	journal	August 2018
Pore Space Partition and Charge Separation in Cage-within-Cage Indium−Organic Frameworks with High CO ₂ Uptake Zheng, Shou-Tian; Bu, Julia T.; Li, Yufei Journal of the American Chemical Society, Vol. 132, Issue 48 https://doi.org/10.1021/ja106903p	journal	December 2010
Two-in-One: Inherent Anhydrous and Water-Assisted High Proton Conduction in a 3D Metal-Organic Framework Nagarkar, Sanjog S.; Unni, Sreekuttan M.; Sharma, Amitosh Angewandte Chemie International Edition, Vol. 53, Issue 10 https://doi.org/10.1002/anie.201309077	journal	December 2013
Quest for Highly Connected Metal–Organic Framework Platforms: Rare-Earth Polynuclear Clusters Versatility Meets Net Topology Needs Alezi, Dalal; Peedikakkal, Abdul Malik P.; Weseliński, Łukasz J. Journal of the American Chemical Society, Vol. 137, Issue 16 https://doi.org/10.1021/jacs.5b00450	journal	April 2015
Modification of the pore environment in UiO-type metal-organic framework toward boosting the separation of propane/propylene He, Chaohui; Wang, Yong; Chen, Yang Chemical Engineering Journal, Vol. 403 https://doi.org/10.1016/j.cej.2020.126428	journal	January 2021
Two-in-One: Inherent Anhydrous and Water-Assisted High Proton Conduction in a 3D Metal-Organic Framework Nagarkar, Sanjog S.; Unni, Sreekuttan M.; Sharma, Amitosh Angewandte Chemie, Vol. 126, Issue 10 https://doi.org/10.1002/ange.201309077	journal	December 2013
Improving MOF stability: approaches and applications Ding, Meili; Cai, Xuechao; Jiang, Hai-Long Chemical Science, Vol. 10, Issue 44 https://doi.org/10.1039/C9SC03916C	journal	January 2019
A Water-Stable Metal–Organic Framework with Highly Acidic Pores for Proton-Conducting Applications Taylor, Jared M.; Dawson, Karl W.; Shimizu, George K. H. Journal of the American Chemical Society, Vol. 135, Issue 4 https://doi.org/10.1021/ja310435e	journal	January 2013
Precise Pore Space Partitions Combined with High‐Density Hydrogen‐Bonding Acceptors within Metal–Organic Frameworks for Highly Efficient Acetylene Storage and Separation Xue, Ying‐Ying; Bai, Xiao‐Ying; Zhang, Jing Angewandte Chemie International Edition, Vol. 60, Issue 18 https://doi.org/10.1002/anie.202015861	journal	March 2021
A NbO-type copper metal–organic framework decorated with carboxylate groups exhibiting highly selective CO ₂ adsorption and separation of organic dyes Liu, Xiuping; Xiao, Zhenyu; Xu, Jing Journal of Materials Chemistry A, Vol. 4, Issue 36 https://doi.org/10.1039/C6TA02908F	journal	January 2016
A Highly Connected Trinuclear Cluster Based Metal–Organic Framework for Efficient Separation of C ₂ H ₂ /C ₂ H ₄ and C ₂ H ₂ /CO ₂ Li, Qian; Wu, Nana; Li, Jia Inorganic Chemistry, Vol. 59, Issue 18 https://doi.org/10.1021/acs.inorgchem.0c02101	journal	September 2020
Design and Synthesis of a Water-Stable Anionic Uranium-Based Metal-Organic Framework (MOF) with Ultra Large Pores Li, Peng; Vermeulen, Nicolaas A.; Gong, Xirui Angewandte Chemie, Vol. 128, Issue 35 https://doi.org/10.1002/ange.201605547	journal	July 2016
A Tale of Two Trimers from Two Different Worlds: A COF-Inspired Synthetic Strategy for Pore-Space Partitioning of MOFs Wang, Yanxiang; Zhao, Xiang; Yang, Huajun Angewandte Chemie International Edition, Vol. 58, Issue 19 https://doi.org/10.1002/anie.201901343	journal	April 2019
Fine-Tuning the Pore Environment of the Microporous Cu-MOF for High Propylene Storage and Efficient Separation of Light Hydrocarbons Fan, Weidong; Wang, Xia; Zhang, Xiurong ACS Central Science, Vol. 5, Issue 7 https://doi.org/10.1021/acscentsci.9b00423	journal	June 2019
Immobilization of Ag( i ) into a metal–organic framework with –SO ₃ H sites for highly selective olefin–paraffin separation at room temperature Chang, Ganggang; Huang, Minhui; Su, Ye Chemical Communications, Vol. 51, Issue 14 https://doi.org/10.1039/C4CC09679G	journal	January 2015
Superprotonic Conductivity of a UiO-66 Framework Functionalized with Sulfonic Acid Groups by Facile Postsynthetic Oxidation Phang, Won Ju; Jo, Hyuna; Lee, Woo Ram Angewandte Chemie, Vol. 127, Issue 17 https://doi.org/10.1002/ange.201411703	journal	February 2015
Benchmark C ₂ H ₂ /CO ₂ Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry Zhang, Ling; Jiang, Ke; Yang, Lifeng Angewandte Chemie International Edition, Vol. 60, Issue 29 https://doi.org/10.1002/anie.202102810	journal	June 2021
Benchmark C ₂ H ₂ /CO ₂ Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry Zhang, Ling; Jiang, Ke; Yang, Lifeng Angewandte Chemie, Vol. 133, Issue 29 https://doi.org/10.1002/ange.202102810	journal	June 2021
Exploring the Influence of Halogen Coordination Effect of Stable Bimetallic MOFs on Oxygen Evolution Reaction Lu, Jia‐Ni; Liu, Jiang; Dong, Long‐Zhang Chemistry – A European Journal, Vol. 25, Issue 69 https://doi.org/10.1002/chem.201903482	journal	October 2019
Precise Pore Space Partitions Combined with High‐Density Hydrogen‐Bonding Acceptors within Metal–Organic Frameworks for Highly Efficient Acetylene Storage and Separation Xue, Ying‐Ying; Bai, Xiao‐Ying; Zhang, Jing Angewandte Chemie, Vol. 133, Issue 18 https://doi.org/10.1002/ange.202015861	journal	March 2021
Superprotonic Conductivity of a UiO-66 Framework Functionalized with Sulfonic Acid Groups by Facile Postsynthetic Oxidation Phang, Won Ju; Jo, Hyuna; Lee, Woo Ram Angewandte Chemie International Edition, Vol. 54, Issue 17 https://doi.org/10.1002/anie.201411703	journal	February 2015
Pore Space Partition within a Metal–Organic Framework for Highly Efficient C ₂ H ₂ /CO ₂ Separation Ye, Yingxiang; Ma, Zhenlin; Lin, Rui-Biao Journal of the American Chemical Society, Vol. 141, Issue 9 https://doi.org/10.1021/jacs.9b00232	journal	February 2019
A flexible metal–organic framework with a high density of sulfonic acid sites for proton conduction Yang, Fan; Xu, Gang; Dou, Yibo Nature Energy, Vol. 2, Issue 11 https://doi.org/10.1038/s41560-017-0018-7	journal	October 2017
Cation-Dependent Nonlinear Optical Behavior in an Octupolar 3D Anionic Metal-Organic Open Framework Liu, Yan; Li, Gao; Li, Xing Angewandte Chemie International Edition, Vol. 46, Issue 33 https://doi.org/10.1002/anie.200701056	journal	July 2007
A Tale of Two Trimers from Two Different Worlds: A COF‐Inspired Synthetic Strategy for Pore‐Space Partitioning of MOFs Wang, Yanxiang; Zhao, Xiang; Yang, Huajun Angewandte Chemie, Vol. 131, Issue 19 https://doi.org/10.1002/ange.201901343	journal	February 2019
A Single-Crystal Open-Capsule Metal–Organic Framework Wei, Yong-Sheng; Zhang, Mei; Kitta, Mitsunori Journal of the American Chemical Society, Vol. 141, Issue 19 https://doi.org/10.1021/jacs.9b02417	journal	April 2019
Unravelling exceptional acetylene and carbon dioxide adsorption within a tetra-amide functionalized metal-organic framework Moreau, Florian; da Silva, Ivan; Al Smail, Nada H. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14085	journal	February 2017
Promotion of Low-Humidity Proton Conduction by Controlling Hydrophilicity in Layered Metal–Organic Frameworks Sadakiyo, Masaaki; O̅kawa, Hisashi; Shigematsu, Akihito Journal of the American Chemical Society, Vol. 134, Issue 12 https://doi.org/10.1021/ja300122r	journal	March 2012
Tunable Rare Earth fcu -MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction Xue, Dong-Xu; Belmabkhout, Youssef; Shekhah, Osama Journal of the American Chemical Society, Vol. 137, Issue 15 https://doi.org/10.1021/ja5131403	journal	April 2015
Ligand Torsion Triggered Two Robust Fe-Tetratopic Carboxylate Frameworks with Enhanced Gas Uptake and Separation Performance Zhang, Jian-Wei; Hu, Man-Cheng; Li, Shu-Ni Chemistry - A European Journal, Vol. 23, Issue 27 https://doi.org/10.1002/chem.201700867	journal	April 2017
Pore-Space-Partition-Enabled Exceptional Ethane Uptake and Ethane-Selective Ethane–Ethylene Separation Yang, Huajun; Wang, Yanxiang; Krishna, Rajamani Journal of the American Chemical Society, Vol. 142, Issue 5 https://doi.org/10.1021/jacs.9b12924	journal	January 2020

Linked Research (4)

Similar Records

Simultaneous Control of Pore‐Space Partition and Charge Distribution in Multi‐Modular Metal–Organic Frameworks

Journal Article · 2022 · Angewandte Chemie · OSTI ID:1845030

Hong, Anh N.; Kusumoputro, Emily; Wang, Yanxiang; +4 more

Concurrent Enhancement of Acetylene Uptake Capacity and Selectivity by Progressive Core Expansion and Extra–Framework Anions in Pore–Space–Partitioned Metal–Organic Frameworks

Journal Article · 2022 · Chemistry - A European Journal · OSTI ID:2205469

Hong, Anh N.; Wang, Yanxiang; Chen, Yichong; +4 more

A Strategy for Constructing Pore-Space-Partitioned MOFs with High Uptake Capacity for C₂ Hydrocarbons and CO₂

Journal Article · 2020 · Angewandte Chemie (International Edition) · OSTI ID:1755101

Wang, Yong; Jia, Xiaoxia; Yang, Huajun; +6 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
stability
anionic
MOFs
gas sorption

CCDC 2124129: Experimental Crystal Structure Determination N., Hong, Anh; Emily, Kusumoputro,; Yanxiang, Wang, https://doi.org/10.5517/ccdc.csd.cc299b98 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2124128: Experimental Crystal Structure Determination N., Hong, Anh; Emily, Kusumoputro,; Yanxiang, Wang, https://doi.org/10.5517/ccdc.csd.cc299b87 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2124127: Experimental Crystal Structure Determination N., Hong, Anh; Emily, Kusumoputro,; Yanxiang, Wang, https://doi.org/10.5517/ccdc.csd.cc299b76 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2124130: Experimental Crystal Structure Determination N., Hong, Anh; Emily, Kusumoputro,; Yanxiang, Wang, https://doi.org/10.5517/ccdc.csd.cc299bb9 The current record is supplemented by this dataset	dataset	January 2022

Title: Simultaneous Control of Pore-Space Partition and Charge Distribution in Multi-Modular Metal–Organic Frameworks

Citation Formats

References (56)

Linked Research (4)

Similar Records

Related Subjects