DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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. https://doi.org/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. https://doi.org/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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 31 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Artificial Photosynthesis: Solar Splitting of Water to Hydrogen and Oxygen
journal, March 1995

  • Bard, Allen J.; Fox, Marye Anne
  • Accounts of Chemical Research, Vol. 28, Issue 3
  • DOI: 10.1021/ar00051a007

Direct splitting of water under visible light irradiation with an oxide semiconductor photocatalyst
journal, December 2001

  • Zou, Zhigang; Ye, Jinhua; Sayama, Kazuhiro
  • Nature, Vol. 414, Issue 6864
  • DOI: 10.1038/414625a

Advanced Nanoarchitectures for Solar Photocatalytic Applications
journal, November 2011

  • Kubacka, Anna; Fernández-García, Marcos; Colón, Gerardo
  • Chemical Reviews, Vol. 112, Issue 3
  • DOI: 10.1021/cr100454n

Engineering coordination polymers for photocatalysis
journal, April 2016


Photoelectrocatalytic reduction of carbon dioxide in aqueous suspensions of semiconductor powders
journal, February 1979

  • Inoue, Tooru; Fujishima, Akira; Konishi, Satoshi
  • Nature, Vol. 277, Issue 5698
  • DOI: 10.1038/277637a0

Effect of Surface Structures on Photocatalytic CO 2 Reduction Using Quantized CdS Nanocrystallites 1
journal, October 1997

  • Fujiwara, Hiroaki; Hosokawa, Hiroji; Murakoshi, Kei
  • The Journal of Physical Chemistry B, Vol. 101, Issue 41
  • DOI: 10.1021/jp971621q

Photoreduction of carbon dioxide using chalcogenide semiconductor microcrystals
journal, February 1995

  • Inoue, Hiroshi; Moriwaki, Hiroshi; Maeda, Kataro
  • Journal of Photochemistry and Photobiology A: Chemistry, Vol. 86, Issue 1-3
  • DOI: 10.1016/1010-6030(94)03936-O

Introduction to Metal–Organic Frameworks
journal, September 2011

  • Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 673-674
  • DOI: 10.1021/cr300014x

Metal–Organic Frameworks (MOFs)
journal, January 2014

  • Zhou, Hong-Cai “Joe”; Kitagawa, Susumu
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS90059F

Metal–organic frameworks for artificial photosynthesis and photocatalysis
journal, January 2014


Stable metal–organic frameworks as a host platform for catalysis and biomimetics
journal, January 2018

  • Qin, Jun-Sheng; Yuan, Shuai; Lollar, Christina
  • Chemical Communications, Vol. 54, Issue 34
  • DOI: 10.1039/C7CC09173G

MOFs-Based Heterogeneous Catalysts: New Opportunities for Energy-Related CO 2 Conversion
journal, October 2018

  • Lei, Zhendong; Xue, Yuancheng; Chen, Wenqian
  • Advanced Energy Materials, Vol. 8, Issue 32
  • DOI: 10.1002/aenm.201801587

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Self-Accelerating CO Sorption in a Soft Nanoporous Crystal
journal, December 2013


Methane storage in metal–organic frameworks
journal, January 2014

  • He, Yabing; Zhou, Wei; Qian, Guodong
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00032C

Recent advances in porous polyoxometalate-based metal–organic framework materials
journal, January 2014

  • Du, Dong-Ying; Qin, Jun-Sheng; Li, Shun-Li
  • Chem. Soc. Rev., Vol. 43, Issue 13
  • DOI: 10.1039/C3CS60404G

Luminescent metal–organic frameworks for chemical sensing and explosive detection
journal, January 2014

  • Hu, Zhichao; Deibert, Benjamin J.; Li, Jing
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00010B

Ultrastable Polymolybdate-Based Metal–Organic Frameworks as Highly Active Electrocatalysts for Hydrogen Generation from Water
journal, May 2015

  • Qin, Jun-Sheng; Du, Dong-Ying; Guan, Wei
  • Journal of the American Chemical Society, Vol. 137, Issue 22
  • DOI: 10.1021/jacs.5b02688

Postsynthetic Tuning of Metal–Organic Frameworks for Targeted Applications
journal, February 2017


Metal–organic and covalent organic frameworks as single-site catalysts
journal, January 2017

  • Rogge, S. M. J.; Bavykina, A.; Hajek, J.
  • Chemical Society Reviews, Vol. 46, Issue 11
  • DOI: 10.1039/C7CS00033B

Derivation and Decoration of Nets with Trigonal-Prismatic Nodes: A Unique Route to Reticular Synthesis of Metal–Organic Frameworks
journal, January 2016

  • Qin, Jun-Sheng; Du, Dong-Ying; Li, Mian
  • Journal of the American Chemical Society, Vol. 138, Issue 16
  • DOI: 10.1021/jacs.6b01093

Design and synthesis of multifunctional metal–organic zeolites
journal, January 2018

  • Tan, Yan-Xi; Wang, Fei; Zhang, Jian
  • Chemical Society Reviews, Vol. 47, Issue 6
  • DOI: 10.1039/C7CS00782E

Doping Metal–Organic Frameworks for Water Oxidation, Carbon Dioxide Reduction, and Organic Photocatalysis
journal, August 2011

  • Wang, Cheng; Xie, Zhigang; deKrafft, Kathryn E.
  • Journal of the American Chemical Society, Vol. 133, Issue 34, p. 13445-13454
  • DOI: 10.1021/ja203564w

Studies on Photocatalytic CO 2 Reduction over NH 2 -Uio-66(Zr) and Its Derivatives: Towards a Better Understanding of Photocatalysis on Metal-Organic Frameworks
journal, September 2013

  • Sun, Dengrong; Fu, Yanghe; Liu, Wenjun
  • Chemistry - A European Journal, Vol. 19, Issue 42
  • DOI: 10.1002/chem.201301728

Visible-Light Photoreduction of CO 2 in a Metal–Organic Framework: Boosting Electron–Hole Separation via Electron Trap States
journal, October 2015

  • Xu, Hai-Qun; Hu, Jiahua; Wang, Dengke
  • Journal of the American Chemical Society, Vol. 137, Issue 42
  • DOI: 10.1021/jacs.5b08773

Photocatalytic CO 2 reduction by a mixed metal (Zr/Ti), mixed ligand metal–organic framework under visible light irradiation
journal, January 2015

  • Lee, Yeob; Kim, Sangjun; Kang, Jeung Ku
  • Chemical Communications, Vol. 51, Issue 26
  • DOI: 10.1039/C5CC00686D

Highly efficient visible-light-driven CO 2 reduction to formate by a new anthracene-based zirconium MOF via dual catalytic routes
journal, January 2016

  • Chen, Dashu; Xing, Hongzhu; Wang, Chungang
  • Journal of Materials Chemistry A, Vol. 4, Issue 7
  • DOI: 10.1039/C6TA00429F

Postsynthetic modification of metal–organic frameworks—a progress report
journal, January 2011

  • Tanabe, Kristine K.; Cohen, Seth M.
  • Chem. Soc. Rev., Vol. 40, Issue 2
  • DOI: 10.1039/C0CS00031K

Beyond post-synthesis modification: evolution of metal–organic frameworks via building block replacement
journal, January 2014

  • Deria, Pravas; Mondloch, Joseph E.; Karagiaridi, Olga
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00067F

Stable Metal–Organic Frameworks with Group 4 Metals: Current Status and Trends
journal, February 2018


Graphenes as Potential Material for Electronics
journal, March 2007

  • Wu, Jishan; Pisula, Wojciech; Müllen, Klaus
  • Chemical Reviews, Vol. 107, Issue 3
  • DOI: 10.1021/cr068010r

New advances in nanographene chemistry
journal, January 2015

  • Narita, Akimitsu; Wang, Xiao-Ye; Feng, Xinliang
  • Chemical Society Reviews, Vol. 44, Issue 18
  • DOI: 10.1039/C5CS00183H

Donor–acceptor conjugated ladder polymer via aromatization-driven thermodynamic annulation
journal, January 2018

  • Lee, Jongbok; Kalin, Alexander J.; Wang, Chenxu
  • Polymer Chemistry, Vol. 9, Issue 13
  • DOI: 10.1039/C7PY02059G

Aromatizing Olefin Metathesis by Ligand Isolation inside a Metal– Organic Framework
journal, September 2013

  • Vermeulen, Nicolaas A.; Karagiaridi, Olga; Sarjeant, Amy A.
  • Journal of the American Chemical Society, Vol. 135, Issue 40
  • DOI: 10.1021/ja407333q

Reticular Chemistry at Its Best: Directed Assembly of Hexagonal Building Units into the Awaited Metal-Organic Framework with the Intricate Polybenzene Topology, pbz-MOF
journal, September 2016

  • Alezi, Dalal; Spanopoulos, Ioannis; Tsangarakis, Constantinos
  • Journal of the American Chemical Society, Vol. 138, Issue 39
  • DOI: 10.1021/jacs.6b08176

Abspaltung aromatisch gebundenen Wasserstoffs und Verknüpfung aromatischer Kerne durch Aluminiumchlorid
journal, January 1912


The Versatile Synthesis and Self-Assembly of Star-Type Hexabenzocoronenes
journal, November 2003

  • Wu, Jishan; Watson, Mark D.; Müllen, Klaus
  • Angewandte Chemie International Edition, Vol. 42, Issue 43
  • DOI: 10.1002/anie.200352047

Single-crystal structure validation with the program PLATON
journal, January 2003


Synthesis and sorption properties of hexa-(peri)-hexabenzocoronene-based porous organic polymers
journal, January 2014

  • Thompson, Christina M.; Li, Fei; Smaldone, Ronald A.
  • Chem. Commun., Vol. 50, Issue 46
  • DOI: 10.1039/C4CC02213K

Hexaphenylbenzene and hexabenzocoronene-based porous polymers for the adsorption of volatile organic compounds
journal, January 2016

  • Karunathilake, Arosha A. K.; Chang, James; Thompson, Christina M.
  • RSC Advances, Vol. 6, Issue 70
  • DOI: 10.1039/C6RA14263J

Methane Adsorption in Metal–Organic Frameworks Containing Nanographene Linkers: A Computational Study
journal, July 2014

  • Bichoutskaia, Elena; Suyetin, Mikhail; Bound, Michelle
  • The Journal of Physical Chemistry C, Vol. 118, Issue 29
  • DOI: 10.1021/jp503210h

A polymeric-semiconductor–metal-complex hybrid photocatalyst for visible-light CO2 reduction
journal, January 2013

  • Maeda, Kazuhiko; Sekizawa, Keita; Ishitani, Osamu
  • Chemical Communications, Vol. 49, Issue 86
  • DOI: 10.1039/c3cc45532g

Introduction of a mediator for enhancing photocatalytic performance via post-synthetic metal exchange in metal–organic frameworks (MOFs)
journal, January 2015

  • Sun, Dengrong; Liu, Wenjun; Qiu, Mei
  • Chemical Communications, Vol. 51, Issue 11
  • DOI: 10.1039/C4CC09407G

Works referencing / citing this record:

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
  • DOI: 10.3390/polym11122090

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

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


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

Recent Advances in Photocatalysis over Metal–Organic Frameworks‐Based Materials
journal, December 2019


Recent Progress on Exploring Stable Metal–Organic Frameworks for Photocatalytic Solar Fuel Production
journal, February 2020


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

Adjustment of the performance and stability of isostructural zeolitic tetrazolate-imidazolate frameworks
journal, January 2020

  • Li, Hai-Zhen; Du, Dong-Ying; Sun, Yayong
  • Dalton Transactions, Vol. 49, Issue 15
  • DOI: 10.1039/d0dt00791a

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


Recent Progress on Exploring Stable Metal–Organic Frameworks for Photocatalytic Solar Fuel Production
journal, August 2020