3-(4-Methylthiophenyl)acetylacetone – ups and downs of flexibility in the synthesis of mixed metal–organic frameworks. Ditopic bridging of hard and soft cations and site-specific desolvation

Hans Gildenast; Stephanie Nölke; Ulli Englert

doi:10.1039/C9CE01932D

3-(4-Methylthiophenyl)acetylacetone – ups and downs of flexibility in the synthesis of mixed metal–organic frameworks. Ditopic bridging of hard and soft cations and site-specific desolvation†

Hans Gildenast,

^a Stephanie Nölke^a and Ulli Englert

*^ab

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* Corresponding authors

^a RWTH Aachen University, Institute of Inorganic Chemistry, Landoltweg 1, 52074 Aachen, Germany
E-mail: ullrich.englert@ac.rwth-aachen.de
Fax: +49 241 8092288
Tel: +49 241 8094666

^b Key Laboratory of Materials for Energy Conversion and Storage, Institute of Molecular Science, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China

Abstract

3-(4-Methylthiophenyl)pentane-2,4-dione (HacacSMePh) combines a Pearson-hard β-diketone and a soft thioether group in its periphery; after deprotonation, it may act as a heterobifunctional linker between metal cations. Coordination of the β-diketo site to trivalent cations afforded a series of M(acacSMePh)₃ metal complexes with dangling thioether moieties. Crosslinking of the mononuclear M(acacSMePh)₃ building units via the SMe functionalities with Ag^I cations resulted in mixed metal–organic frameworks (MMOFs). All bimetallic networks with M^III = Co, Al, Cr, Fe, Ga are isostructural. Statistical occupancy of the M^III site by two different cations may be possible and has been proven for Al^III and Ga^III. The MMOFs are semiporous and contain two co-crystallized chloroform molecules in the asymmetric unit. One of these CHCl₃ molecules may be partially removed while maintaining the structural integrity of the network.

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DOI: https://doi.org/10.1039/C9CE01932D
Article type: Paper
Submitted: 05 Dec 2019
Accepted: 06 Jan 2020
First published: 06 Jan 2020

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CrystEngComm, 2020,22, 1041-1049

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3-(4-Methylthiophenyl)acetylacetone – ups and downs of flexibility in the synthesis of mixed metal–organic frameworks. Ditopic bridging of hard and soft cations and site-specific desolvation

H. Gildenast, S. Nölke and U. Englert, CrystEngComm, 2020, 22, 1041 DOI: 10.1039/C9CE01932D

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CrystEngComm

3-(4-Methylthiophenyl)acetylacetone – ups and downs of flexibility in the synthesis of mixed metal–organic frameworks. Ditopic bridging of hard and soft cations and site-specific desolvation†

Abstract

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3-(4-Methylthiophenyl)acetylacetone – ups and downs of flexibility in the synthesis of mixed metal–organic frameworks. Ditopic bridging of hard and soft cations and site-specific desolvation

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