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, 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.

Authors:

Qin, Jun-Sheng ^[1]; Yuan, Shuai ^[2]; Zhang, Lei ^[3]; Li, Bao  ^[4];

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Du, Dong-Ying ^[5]; Huang, Ning  ^[4];

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Guan, Wei  ^[5];

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Drake, Hannah F. ^[4]; Pang, Jiandong ^[4]; Lan, Ya-Qian  ^[3];

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Alsalme, Ali ^[6]; Zhou, Hong-Cai  ^[7]

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+ Show Author Affiliations

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:

2019-01-09

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