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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.8b11042· OSTI ID:1566593
 [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)
+ Show Author Affiliations

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.

Research Organization:
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 Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Fossil Energy (FE)
Grant/Contract Number:
FE0026472; SC0001015
OSTI ID:
1566593
Journal Information:
Journal of the American Chemical Society, Vol. 141, Issue 5; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 96 works
Citation information provided by
Web of Science

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Cited By (12)

Recent Innovation of Metal-Organic Frameworks for Carbon Dioxide Photocatalytic Reduction journal December 2019
Development of a new Lindqvist-like Fe6 cluster secondary building unit for MOFs journal January 2019
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
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
A Rigid Trigonal-Prismatic Hexagold Metallocage That Behaves as a Coronene Trap journal April 2019
Adjustment of the performance and stability of isostructural zeolitic tetrazolate-imidazolate frameworks journal January 2020
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
BODIPY-Decorated Nanoscale Covalent Organic Frameworks for Photodynamic Therapy journal April 2019

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