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Title: Enhancing Pore-Environment Complexity Using a Trapezoidal Linker: Toward Stepwise Assembly of Multivariate Quinary Metal–Organic Frameworks

Abstract

Multicomponent metal–organic frameworks (MOFs) promise the precise placement of synergistic functional groups with atomic-level precision, capable of promoting fascinating developments in basic sciences and applications. However, the complexity of multicomponent systems poses a challenge to their structural design and synthesis. Herein, we show that linkers of low symmetry can bring new opportunities to the construction of multicomponent MOFs. A carbazole-tetracarboxylate linker of Cs point group symmetry was designed and combined with an 8-connected Zr6 cluster to generate a low-symmetry MOF, PCN-609. PCN-609 contains coordinatively unsaturated Zr sites arranged within a lattice with three crystallographically distinct pockets, which can accommodate linear linkers of different lengths. Sequential linker installation was carried out to postsynthetically insert three linear linkers into PCN-609, giving rise to a quinary MOF. At last, functionalization of each linker from the quinary MOF system creates multivariate pore environments with unprecedented complexity.

Authors:
 [1]; ORCiD logo [2];  [2];  [3];  [2];  [2]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [2]
  1. Texas A & M Univ., College Station, TX (United States); Chinese Academy of Sciences, Fujian (China)
  2. Texas A & M Univ., College Station, TX (United States)
  3. Chinese Academy of Sciences, Fujian (China)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Texas A & M Univ., College Station, TX (United States); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1566589
Grant/Contract Number:  
FE0026472; SC0001015
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 39; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Pang, Jiandong, Yuan, Shuai, Qin, Junsheng, Wu, Mingyan, Lollar, Christina T., Li, Jialuo, Huang, Ning, Li, Bao, Zhang, Peng, and Zhou, Hong -Cai. Enhancing Pore-Environment Complexity Using a Trapezoidal Linker: Toward Stepwise Assembly of Multivariate Quinary Metal–Organic Frameworks. United States: N. p., 2018. Web. doi:10.1021/jacs.8b07411.
Pang, Jiandong, Yuan, Shuai, Qin, Junsheng, Wu, Mingyan, Lollar, Christina T., Li, Jialuo, Huang, Ning, Li, Bao, Zhang, Peng, & Zhou, Hong -Cai. Enhancing Pore-Environment Complexity Using a Trapezoidal Linker: Toward Stepwise Assembly of Multivariate Quinary Metal–Organic Frameworks. United States. doi:https://doi.org/10.1021/jacs.8b07411
Pang, Jiandong, Yuan, Shuai, Qin, Junsheng, Wu, Mingyan, Lollar, Christina T., Li, Jialuo, Huang, Ning, Li, Bao, Zhang, Peng, and Zhou, Hong -Cai. Wed . "Enhancing Pore-Environment Complexity Using a Trapezoidal Linker: Toward Stepwise Assembly of Multivariate Quinary Metal–Organic Frameworks". United States. doi:https://doi.org/10.1021/jacs.8b07411. https://www.osti.gov/servlets/purl/1566589.
@article{osti_1566589,
title = {Enhancing Pore-Environment Complexity Using a Trapezoidal Linker: Toward Stepwise Assembly of Multivariate Quinary Metal–Organic Frameworks},
author = {Pang, Jiandong and Yuan, Shuai and Qin, Junsheng and Wu, Mingyan and Lollar, Christina T. and Li, Jialuo and Huang, Ning and Li, Bao and Zhang, Peng and Zhou, Hong -Cai},
abstractNote = {Multicomponent metal–organic frameworks (MOFs) promise the precise placement of synergistic functional groups with atomic-level precision, capable of promoting fascinating developments in basic sciences and applications. However, the complexity of multicomponent systems poses a challenge to their structural design and synthesis. Herein, we show that linkers of low symmetry can bring new opportunities to the construction of multicomponent MOFs. A carbazole-tetracarboxylate linker of Cs point group symmetry was designed and combined with an 8-connected Zr6 cluster to generate a low-symmetry MOF, PCN-609. PCN-609 contains coordinatively unsaturated Zr sites arranged within a lattice with three crystallographically distinct pockets, which can accommodate linear linkers of different lengths. Sequential linker installation was carried out to postsynthetically insert three linear linkers into PCN-609, giving rise to a quinary MOF. At last, functionalization of each linker from the quinary MOF system creates multivariate pore environments with unprecedented complexity.},
doi = {10.1021/jacs.8b07411},
journal = {Journal of the American Chemical Society},
number = 39,
volume = 140,
place = {United States},
year = {2018},
month = {9}
}

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Works referencing / citing this record:

Zeolite-Type Metal Oxalate Frameworks
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journal, March 2019

  • Tu, Binbin; Diestel, Lisa; Shi, Zhao-Lin
  • Angewandte Chemie International Edition, Vol. 58, Issue 16
  • DOI: 10.1002/anie.201900863

Hierarchical nickel/phosphorus/nitrogen/carbon composites templated by one metal–organic framework as highly efficient supercapacitor electrode materials
journal, January 2019

  • Yu, Fan; Xiong, Xin; Zhou, Liu-Yin
  • Journal of Materials Chemistry A, Vol. 7, Issue 6
  • DOI: 10.1039/c8ta11568k

Structural tuning of zinc–porphyrin frameworks via auxiliary nitrogen-containing ligands towards selective adsorption of cationic dyes
journal, January 2019

  • Wang, Xiao-Ning; Li, Jiang-Li; Zhao, Yu-Meng
  • Chemical Communications, Vol. 55, Issue 46
  • DOI: 10.1039/c9cc02405k

Highly open chalcogenide frameworks built from unusual defective supertetrahedral clusters
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  • Yi, Fei-Yan; Yang, Huajun; Zhao, Xiang
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  • DOI: 10.1002/anie.201900106

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