Title: Control the Structure of Zr-Tetracarboxylate Frameworks through Steric Tuning

Abstract

Ligands with flexible conformations add to the structural diversity of metal–organic frameworks but, at the same time, pose a challenge to structural design and prediction. Representative examples include Zr-tetracarboxylate-based MOFs, which afford assorted structures for a wide range of applications, but also complicate the structural control. Herein, we systematically studied the formation mechanism of a series of (4,8)-connected Zr-tetracarboxylate-based MOFs by altering the substituents on different positions of the organic linkers. Different ligand rotamers give rise to three types of structures with flu, scu, and csq topologies. A combination of experiment and molecular simulation indicate that the steric hindrance of the substituents at different positions dictates the resulting MOF structures. Additionally, the controllable formation of different structures was successfully implemented by a combination of linkers with different steric effects at specific positions.

Authors:

Pang, Jiandong ^[1]; Yuan, Shuai ^[2]; Qin, Junsheng ^[2]; Liu, Caiping ^[3]; Lollar, Christina ^[2]; Wu, Mingyan ^[3]; Yuan, Daqiang  ^[3];

• Search DOE PAGES for author "Yuan, Daqiang"
• Search DOE PAGES for ORCID "0000-0003-4627-072X"

Zhou, Hong-Cai  ^[2];

• Search DOE PAGES for author "Zhou, Hong-Cai"
• Search DOE PAGES for ORCID "0000-0002-9029-3788"

Hong, Maochun ^[3]

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+ Show Author Affiliations

1. Chinese Academy of Sciences (CAS), Beijing (China). State Key Lab. of Structure Chemistry, Fujian Inst. of Research on the Structure of Matter; Texas A & M Univ., College Station, TX (United States). Dept of Chemistry
2. Texas A & M Univ., College Station, TX (United States). Dept of Chemistry
3. Chinese Academy of Sciences (CAS), Beijing (China). State Key Lab. of Structure Chemistry, Fujian Inst. of Research on the Structure of Matter

Publication Date:

Tue Nov 07 00:00:00 EST 2017

Research Org.:

Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)

Sponsoring Org.:

USDOE Office of Fossil Energy (FE)

OSTI Identifier:

1470030

Grant/Contract Number:  

SC0001015

Resource Type:

Accepted Manuscript

Journal Name:

Journal of the American Chemical Society

Additional Journal Information:

Journal Volume: 139; Journal Issue: 46; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; Journal ID: ISSN 0002-7863

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)