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Construction of Highly Proton-Conductive Zr(IV)-Based Metal-Organic Frameworks From Pyrrolo-pyrrole-Based Linkers with a Rhombic Shape.
- Source :
-
Inorganic chemistry [Inorg Chem] 2021 Aug 16; Vol. 60 (16), pp. 12129-12135. Date of Electronic Publication: 2021 Jul 26. - Publication Year :
- 2021
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Abstract
- To date, numerous zirconium cluster-based metal-organic frameworks (Zr-MOFs) with attractive physical properties have been achieved thanks to tailorable organic linkers and versatile Zr clusters. Nevertheless, in comparison with the most-used high-symmetry organic linkers, low-symmetry linkers have rarely been exploited in the construction of Zr-MOFs. Despite challenges in predicting the structure and topology of the MOF, linker desymmetrization presents opportunities for the design of Zr-MOFs with unusual topologies and unexpected functionalities. Herein, we report for the first time the construction of two robust Zr-MOFs ( IAM-7 and IAM-8 ) from two pyrrolo-pyrrole-based low-symmetry tetracarboxylate linkers with a rare rhombic shape. The low symmetry of the linkers arises from the asymmetric pyrrolo-pyrrole core and the varying branch lengths, which play a critical role in the structural diversity between IAM-7 and IAM-8 seen from the structural analysis and lead to hydrophilic channels that contain uncoordinated carboxylate groups in the structure of IAM-7 . Furthermore, the proton conductivity of IAM-7 displays a high temperature and humidity dependence where the proton conductivity increases from 2.84 × 10 <superscript>-8</superscript> S cm <superscript>-1</superscript> at 30 °C and 40% relative humidity (RH) to 1.42 × 10 <superscript>-2</superscript> S cm <superscript>-1</superscript> at 90 °C and 95% RH, making it among one of the most conductive Zr-MOFs. This work not only enriches the library of Zr-MOFs but also offers a platform for the design of low-symmetry linkers toward the structural diversity or irregularity of MOFs as well as their structure-related properties.
Details
- Language :
- English
- ISSN :
- 1520-510X
- Volume :
- 60
- Issue :
- 16
- Database :
- MEDLINE
- Journal :
- Inorganic chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 34310114
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.1c01336