X-ray Electron Density Study of the Chemical Bonding Origin of Glass Formation in Metal–Organic Frameworks

Sounak Sarkar; Thomas Bjørn Egede Grønbech; Aref Mamakhel; Martin Bondesgaard; Kunihisa Sugimoto; Eiji Nishibori; Bo Brummerstedt Iversen

doi:10.1002/anie.202202742

X-ray Electron Density Study of the Chemical Bonding Origin of Glass Formation in Metal–Organic Frameworks

Sounak Sarkar, Thomas Bjørn Egede Grønbech, Aref Mamakhel, Martin Bondesgaard, Kunihisa Sugimoto, Eiji Nishibori, Bo Brummerstedt Iversen^*

^*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

13 Citations (Scopus)

Abstract

Glass-forming metal–organic frameworks (MOFs) have novel applications, but the origin of their peculiar melting behavior is unclear. Here, we report synchrotron X-ray diffraction electron densities of two zeolitic imidazolate frameworks (ZIFs), the glass-forming Zn-ZIF-zni and the isostructural thermally decomposing Co-ZIF-zni. Electron density analysis shows that the Zn−N bonds are more ionic than the Co−N bonds, which have distinct covalent features. Variable-temperature Raman spectra reveal the onset of significant imidazolate bond weakening in Co-ZIF-zni above 673 K. Melting can be controlled by tuning the metal–ligand and imidazole bonding strength as shown from thermal analysis of nine solid-solution Co_xZn_1−x-ZIF-zni (x=0.3 to 0.003) MOFs, and a mere 4 % Co-doping into Zn-ZIF-zni results in thermal decomposition instead of melting. The present findings demonstrate the key role of the metal–ligand bonds and imidazolate bonds in controlling the delicate balance between melting and decomposition processes in this class of ZIF compounds.

Original language	English
Article number	202202742
Journal	Angewandte Chemie - International Edition
Volume	61
Issue	22
Number of pages	8
ISSN	1433-7851
DOIs	https://doi.org/10.1002/anie.202202742
Publication status	Published - May 2022

Keywords

Chemical Bonding
Doping
Electron Density
Melting
Metal–Organic Frameworks
CHARGE-DENSITY
Metal-Organic Frameworks
AMORPHIZATION
LIQUID
CHEMISTRY

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https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9313623/pdf/ANIE-61-0.pdfLicence: CC BY-NC-ND

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title = "X-ray Electron Density Study of the Chemical Bonding Origin of Glass Formation in Metal–Organic Frameworks",

abstract = "Glass-forming metal–organic frameworks (MOFs) have novel applications, but the origin of their peculiar melting behavior is unclear. Here, we report synchrotron X-ray diffraction electron densities of two zeolitic imidazolate frameworks (ZIFs), the glass-forming Zn-ZIF-zni and the isostructural thermally decomposing Co-ZIF-zni. Electron density analysis shows that the Zn−N bonds are more ionic than the Co−N bonds, which have distinct covalent features. Variable-temperature Raman spectra reveal the onset of significant imidazolate bond weakening in Co-ZIF-zni above 673 K. Melting can be controlled by tuning the metal–ligand and imidazole bonding strength as shown from thermal analysis of nine solid-solution CoxZn1−x-ZIF-zni (x=0.3 to 0.003) MOFs, and a mere 4 % Co-doping into Zn-ZIF-zni results in thermal decomposition instead of melting. The present findings demonstrate the key role of the metal–ligand bonds and imidazolate bonds in controlling the delicate balance between melting and decomposition processes in this class of ZIF compounds.",

keywords = "Chemical Bonding, Doping, Electron Density, Melting, Metal–Organic Frameworks, CHARGE-DENSITY, Metal-Organic Frameworks, AMORPHIZATION, LIQUID, CHEMISTRY",

author = "Sounak Sarkar and Gr{\o}nbech, {Thomas Bj{\o}rn Egede} and Aref Mamakhel and Martin Bondesgaard and Kunihisa Sugimoto and Eiji Nishibori and Iversen, {Bo Brummerstedt}",

note = "Publisher Copyright: {\textcopyright} 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2022",

month = may,

doi = "10.1002/anie.202202742",

language = "English",

volume = "61",

journal = "Angewandte Chemie - International Edition",

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X-ray Electron Density Study of the Chemical Bonding Origin of Glass Formation in Metal–Organic Frameworks. / Sarkar, Sounak; Grønbech, Thomas Bjørn Egede; Mamakhel, Aref et al.
In: Angewandte Chemie - International Edition, Vol. 61, No. 22, 202202742, 05.2022.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

TY - JOUR

T1 - X-ray Electron Density Study of the Chemical Bonding Origin of Glass Formation in Metal–Organic Frameworks

AU - Sarkar, Sounak

AU - Grønbech, Thomas Bjørn Egede

AU - Mamakhel, Aref

AU - Bondesgaard, Martin

AU - Sugimoto, Kunihisa

AU - Nishibori, Eiji

AU - Iversen, Bo Brummerstedt

PY - 2022/5

Y1 - 2022/5

N2 - Glass-forming metal–organic frameworks (MOFs) have novel applications, but the origin of their peculiar melting behavior is unclear. Here, we report synchrotron X-ray diffraction electron densities of two zeolitic imidazolate frameworks (ZIFs), the glass-forming Zn-ZIF-zni and the isostructural thermally decomposing Co-ZIF-zni. Electron density analysis shows that the Zn−N bonds are more ionic than the Co−N bonds, which have distinct covalent features. Variable-temperature Raman spectra reveal the onset of significant imidazolate bond weakening in Co-ZIF-zni above 673 K. Melting can be controlled by tuning the metal–ligand and imidazole bonding strength as shown from thermal analysis of nine solid-solution CoxZn1−x-ZIF-zni (x=0.3 to 0.003) MOFs, and a mere 4 % Co-doping into Zn-ZIF-zni results in thermal decomposition instead of melting. The present findings demonstrate the key role of the metal–ligand bonds and imidazolate bonds in controlling the delicate balance between melting and decomposition processes in this class of ZIF compounds.

AB - Glass-forming metal–organic frameworks (MOFs) have novel applications, but the origin of their peculiar melting behavior is unclear. Here, we report synchrotron X-ray diffraction electron densities of two zeolitic imidazolate frameworks (ZIFs), the glass-forming Zn-ZIF-zni and the isostructural thermally decomposing Co-ZIF-zni. Electron density analysis shows that the Zn−N bonds are more ionic than the Co−N bonds, which have distinct covalent features. Variable-temperature Raman spectra reveal the onset of significant imidazolate bond weakening in Co-ZIF-zni above 673 K. Melting can be controlled by tuning the metal–ligand and imidazole bonding strength as shown from thermal analysis of nine solid-solution CoxZn1−x-ZIF-zni (x=0.3 to 0.003) MOFs, and a mere 4 % Co-doping into Zn-ZIF-zni results in thermal decomposition instead of melting. The present findings demonstrate the key role of the metal–ligand bonds and imidazolate bonds in controlling the delicate balance between melting and decomposition processes in this class of ZIF compounds.

KW - Chemical Bonding

KW - Doping

KW - Electron Density

KW - Melting

KW - Metal–Organic Frameworks

KW - CHARGE-DENSITY

KW - Metal-Organic Frameworks

KW - AMORPHIZATION

KW - LIQUID

KW - CHEMISTRY

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U2 - 10.1002/anie.202202742

DO - 10.1002/anie.202202742

M3 - Journal article

C2 - 35286738

AN - SCOPUS:85127296486

SN - 1433-7851

VL - 61

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 22

M1 - 202202742

ER -

X-ray Electron Density Study of the Chemical Bonding Origin of Glass Formation in Metal–Organic Frameworks

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