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Title: Creating Well-Defined Hexabenzocoronene in Zirconium Metal–Organic Framework by Postsynthetic Annulation

Abstract

The incorporation of large π-conjugated ligands into metal–organic frameworks (MOFs) can present interesting photophysical and electrochemical properties into the framework. However, these effects are often hindered by the strong π–π interaction and the low solubility of the arylated ligands. Herein, we report the synthesis of a porous zirconium-based MOF, Zr63-O)43-OH)4(OH)6(H2O)6(HCHC) (PCN-136, HCHC = hexakis(4-carboxyphenyl)hexabenzocoronene), which is composed of a hexacarboxylate linker with a π-conjugated hexabenzocoronene moiety. Direct assembly of the Zr4+ metal centers and the HCHC ligands was unsuccessful due to the low solubility and the unfavorable conformation of the arylated HCHC ligand. Hence, PCN-136 was obtained from aromatization-driven postsynthetic annulation of the hexaphenylbenzene fragment in a preformed framework (pbz-MOF-1) to avoid π–π stacking. This postsynthetic modification was done through a single-crystal-to-single-crystal transformation and was clearly observable utilizing single -crystal X-ray crystallography. The formation of large π-conjugated systems on the organic linker dramatically enhanced the photoresponsive properties of PCN-136. With isolated hexabenzocoronene moieties as photosensitizers and Zr–oxo clusters as catalytic sites, PCN-136 was employed as an inherent photocatalytic system for CO2 reduction under visible-light irradiation, which showed increased activity compared with pbz-MOF-1.

Authors:
 [1];  [2];  [3]; ORCiD logo [4];  [5]; ORCiD logo [4]; ORCiD logo [5];  [4];  [4]; ORCiD logo [3];  [6]; ORCiD logo [7]
  1. Texas A & M Univ., College Station, TX (United States); Jilin Univ., Changchun (China)
  2. Texas A & M Univ., College Station, TX (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  3. Nanjing Univ. (China)
  4. Texas A & M Univ., College Station, TX (United States)
  5. Northeast Normal Univ., Changchun (China)
  6. King Saud Univ., Riyadh (Saudi Arabia)
  7. Texas A & M Univ., College Station, TX (United States); King Saud Univ., Riyadh (Saudi Arabia)
Publication Date:
Research Org.:
Univ. of California, Berkeley, CA (United States). Energy Frontier Research Center (EFRC) Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Texas A & M Univ., College Station, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1566593
Grant/Contract Number:  
FE0026472; SC0001015
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 5; 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

Citation Formats

Qin, Jun-Sheng, Yuan, Shuai, Zhang, Lei, Li, Bao, Du, Dong-Ying, Huang, Ning, Guan, Wei, Drake, Hannah F., Pang, Jiandong, Lan, Ya-Qian, Alsalme, Ali, and Zhou, Hong-Cai. Creating Well-Defined Hexabenzocoronene in Zirconium Metal–Organic Framework by Postsynthetic Annulation. United States: N. p., 2019. Web. doi:10.1021/jacs.8b11042.
Qin, Jun-Sheng, Yuan, Shuai, Zhang, Lei, Li, Bao, Du, Dong-Ying, Huang, Ning, Guan, Wei, Drake, Hannah F., Pang, Jiandong, Lan, Ya-Qian, Alsalme, Ali, & Zhou, Hong-Cai. Creating Well-Defined Hexabenzocoronene in Zirconium Metal–Organic Framework by Postsynthetic Annulation. United States. doi:10.1021/jacs.8b11042.
Qin, Jun-Sheng, Yuan, Shuai, Zhang, Lei, Li, Bao, Du, Dong-Ying, Huang, Ning, Guan, Wei, Drake, Hannah F., Pang, Jiandong, Lan, Ya-Qian, Alsalme, Ali, and Zhou, Hong-Cai. Wed . "Creating Well-Defined Hexabenzocoronene in Zirconium Metal–Organic Framework by Postsynthetic Annulation". United States. doi:10.1021/jacs.8b11042. https://www.osti.gov/servlets/purl/1566593.
@article{osti_1566593,
title = {Creating Well-Defined Hexabenzocoronene in Zirconium Metal–Organic Framework by Postsynthetic Annulation},
author = {Qin, Jun-Sheng and Yuan, Shuai and Zhang, Lei and Li, Bao and Du, Dong-Ying and Huang, Ning and Guan, Wei and Drake, Hannah F. and Pang, Jiandong and Lan, Ya-Qian and Alsalme, Ali and Zhou, Hong-Cai},
abstractNote = {The incorporation of large π-conjugated ligands into metal–organic frameworks (MOFs) can present interesting photophysical and electrochemical properties into the framework. However, these effects are often hindered by the strong π–π interaction and the low solubility of the arylated ligands. Herein, we report the synthesis of a porous zirconium-based MOF, Zr6(μ3-O)4(μ3-OH)4(OH)6(H2O)6(HCHC) (PCN-136, HCHC = hexakis(4-carboxyphenyl)hexabenzocoronene), which is composed of a hexacarboxylate linker with a π-conjugated hexabenzocoronene moiety. Direct assembly of the Zr4+ metal centers and the HCHC ligands was unsuccessful due to the low solubility and the unfavorable conformation of the arylated HCHC ligand. Hence, PCN-136 was obtained from aromatization-driven postsynthetic annulation of the hexaphenylbenzene fragment in a preformed framework (pbz-MOF-1) to avoid π–π stacking. This postsynthetic modification was done through a single-crystal-to-single-crystal transformation and was clearly observable utilizing single -crystal X-ray crystallography. The formation of large π-conjugated systems on the organic linker dramatically enhanced the photoresponsive properties of PCN-136. With isolated hexabenzocoronene moieties as photosensitizers and Zr–oxo clusters as catalytic sites, PCN-136 was employed as an inherent photocatalytic system for CO2 reduction under visible-light irradiation, which showed increased activity compared with pbz-MOF-1.},
doi = {10.1021/jacs.8b11042},
journal = {Journal of the American Chemical Society},
number = 5,
volume = 141,
place = {United States},
year = {2019},
month = {1}
}

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Works referencing / citing this record:

A Tale of Two Trimers from Two Different Worlds: A COF-Inspired Synthetic Strategy for Pore-Space Partitioning of MOFs
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A Rigid Trigonal-Prismatic Hexagold Metallocage That Behaves as a Coronene Trap
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  • Ibáñez, Susana; Peris, Eduardo
  • Angewandte Chemie International Edition, Vol. 58, Issue 20
  • DOI: 10.1002/anie.201902568

Development of a new Lindqvist-like Fe6 cluster secondary building unit for MOFs
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  • Lin, Li-Dan; Li, Zhong; Zhao, Dan
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  • DOI: 10.1039/c9cc04999a

Highly open chalcogenide frameworks built from unusual defective supertetrahedral clusters
journal, January 2019

  • Xue, Chaozhuang; Zhang, Li; Wang, Xiaoli
  • Dalton Transactions, Vol. 48, Issue 29
  • DOI: 10.1039/c9dt01754b

A Tale of Two Trimers from Two Different Worlds: A COF-Inspired Synthetic Strategy for Pore-Space Partitioning of MOFs
journal, April 2019

  • Wang, Yanxiang; Zhao, Xiang; Yang, Huajun
  • Angewandte Chemie International Edition, Vol. 58, Issue 19
  • DOI: 10.1002/anie.201901343

A Rigid Trigonal-Prismatic Hexagold Metallocage That Behaves as a Coronene Trap
journal, April 2019

  • Ibáñez, Susana; Peris, Eduardo
  • Angewandte Chemie International Edition, Vol. 58, Issue 20
  • DOI: 10.1002/anie.201902568

Development of a new Lindqvist-like Fe6 cluster secondary building unit for MOFs
journal, January 2019

  • Lin, Li-Dan; Li, Zhong; Zhao, Dan
  • Chemical Communications, Vol. 55, Issue 72
  • DOI: 10.1039/c9cc04999a

Highly open chalcogenide frameworks built from unusual defective supertetrahedral clusters
journal, January 2019

  • Xue, Chaozhuang; Zhang, Li; Wang, Xiaoli
  • Dalton Transactions, Vol. 48, Issue 29
  • DOI: 10.1039/c9dt01754b

A Tale of Two Trimers from Two Different Worlds: A COF‐Inspired Synthetic Strategy for Pore‐Space Partitioning of MOFs
journal, February 2019


A Rigid Trigonal‐Prismatic Hexagold Metallocage That Behaves as a Coronene Trap
journal, April 2019


Recent Advances in Photocatalysis over Metal–Organic Frameworks‐Based Materials
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Recent Progress on Exploring Stable Metal–Organic Frameworks for Photocatalytic Solar Fuel Production
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Adjustment of the performance and stability of isostructural zeolitic tetrazolate-imidazolate frameworks
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  • Li, Hai-Zhen; Du, Dong-Ying; Sun, Yayong
  • Dalton Transactions, Vol. 49, Issue 15
  • DOI: 10.1039/d0dt00791a

Recent Innovation of Metal-Organic Frameworks for Carbon Dioxide Photocatalytic Reduction
journal, December 2019

  • Kidanemariam, Alemayehu; Lee, Jiwon; Park, Juhyun
  • Polymers, Vol. 11, Issue 12
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