Determining Linker Ratios of Mixed Metal-Organic Frameworks via Magnetic Susceptibility Measurements

Fuente: arXiv
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Main Authors: Du, Na, Zhao, Miao Miao, Wang, Xintian, Zhao, Yan, Yang, Yang, Zhu, Yu Ying, Wang, Ruo Tong, Ren, Peng, Yen, Fei
Format: Preprint
Published: 2025
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author Du, Na
Zhao, Miao Miao
Wang, Xintian
Zhao, Yan
Yang, Yang
Zhu, Yu Ying
Wang, Ruo Tong
Ren, Peng
Yen, Fei
author_facet Du, Na
Zhao, Miao Miao
Wang, Xintian
Zhao, Yan
Yang, Yang
Zhu, Yu Ying
Wang, Ruo Tong
Ren, Peng
Yen, Fei
contents Partial replacement of the organic linkers of metal-organic frameworks (MOFs) often optimizes their functionalities, however, accurate characterization of their molar ratios in many cases is challenging. This work presents a method of determining such linker ratios via measurements of the magnetic susceptibility of small quantities of powdered samples. The main presumption is taking the diamagnetic and paramagnetic contributions to the molar magnetic susceptibility of the two parent MOFs to be additive. To verify this, four examples are provided with commonly used MOFs to represent the cases when both parent MOFs are either paramagnetic or diamagnetic but with different linkers with the following systems: [MIL-101(Cr)-SO$_3$H]$_{(1-δ)}$[MIL-101(Cr)-NO$_2$]$_δ$, [EuMOF]$_{(1-δ)}$[EuPDCA]$_δ$, [UiO-66-COOH]$_{(1-δ)}$[UiO-66]$_δ$ and [MIL-101(Cr) F Free]$_{(1-δ)}$[MIL-53(Al)]$_δ$, where 1-$δ$ : $δ$ are the ratios to be determined. Depending on whether the systems were strictly paramagnetic, strictly diamagnetic or mixed, the experimental error of $δ$ ranged between 0.00002 and 0.012, respectively. We expect the presented method to be widely employed since samples only need to be in powdered form and because there is a lack of characterization tools in the area of MOF linker ratios. The presented method is also applicable to resolving the ratios of mixed ordinary paramagnetic systems as well as other types of non-magnetic composite materials such as tapes, zeolites and thin films.
format Preprint
id arxiv_https___arxiv_org_abs_2505_06876
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Determining Linker Ratios of Mixed Metal-Organic Frameworks via Magnetic Susceptibility Measurements
Du, Na
Zhao, Miao Miao
Wang, Xintian
Zhao, Yan
Yang, Yang
Zhu, Yu Ying
Wang, Ruo Tong
Ren, Peng
Yen, Fei
Materials Science
Chemical Physics
Partial replacement of the organic linkers of metal-organic frameworks (MOFs) often optimizes their functionalities, however, accurate characterization of their molar ratios in many cases is challenging. This work presents a method of determining such linker ratios via measurements of the magnetic susceptibility of small quantities of powdered samples. The main presumption is taking the diamagnetic and paramagnetic contributions to the molar magnetic susceptibility of the two parent MOFs to be additive. To verify this, four examples are provided with commonly used MOFs to represent the cases when both parent MOFs are either paramagnetic or diamagnetic but with different linkers with the following systems: [MIL-101(Cr)-SO$_3$H]$_{(1-δ)}$[MIL-101(Cr)-NO$_2$]$_δ$, [EuMOF]$_{(1-δ)}$[EuPDCA]$_δ$, [UiO-66-COOH]$_{(1-δ)}$[UiO-66]$_δ$ and [MIL-101(Cr) F Free]$_{(1-δ)}$[MIL-53(Al)]$_δ$, where 1-$δ$ : $δ$ are the ratios to be determined. Depending on whether the systems were strictly paramagnetic, strictly diamagnetic or mixed, the experimental error of $δ$ ranged between 0.00002 and 0.012, respectively. We expect the presented method to be widely employed since samples only need to be in powdered form and because there is a lack of characterization tools in the area of MOF linker ratios. The presented method is also applicable to resolving the ratios of mixed ordinary paramagnetic systems as well as other types of non-magnetic composite materials such as tapes, zeolites and thin films.
title Determining Linker Ratios of Mixed Metal-Organic Frameworks via Magnetic Susceptibility Measurements
topic Materials Science
Chemical Physics
url https://arxiv.org/abs/2505.06876