Influence of Substituents in Terephthalate Linker on the Structure of MOFs Obtained from Presynthesized Heterometallic Complex

Marina Barsukova,Denis Samsonenko,Evgeny Dudko,Alexey Ryadun,Vladimir Fedin,Konstantin Kovalenko,Aleksandr Sapianik

doi:10.3390/inorganics9010004

Marina Barsukova, Denis Samsonenko + Show 5 more

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https://doi.org/10.3390/inorganics9010004

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Abstract

The synthesis of new porous materials with desired properties is a challenging task. It becomes especially difficult if you need to combine several metals in one framework to obtain a heterometallic node. The use of presynthesized complexes for obtaining of new heterometallic metal–organic frameworks could be essential to solve the problem of tailored synthesis. In our study we use presynthesized heterometallic pivalate complex [Li2Zn2(piv)6(py)2] to obtain new MOFs with heterometallic core as a node of the framework. We are managed to obtain four new heterometallic MOFs: [H2N(CH3)2]2[Li2Zn2(bdc)4]·CH3CN·DMF (1), [Li2Zn2(H2Br2-bdc)(Br2-bdc)3]·2DMF (2), [H2N(CH3)2][LiZn2(ndc)3]·CH3CN (3) and [{Li2Zn2(dmf)(py)2}{LiZn(dmf)2}2 (NO2-bdc)6]·5DMF (4). Moreover three of them contain starting tetranuclear core {Li2Zn2} and saves its geometry. We also demonstrate the influence of substituent in terephthalate ring on preservation of tetranuclear core. For compound 1 it was shown that luminescence of the framework could be quenched when nitrobenzene is included in the pores.

Highlights

Metal–organic frameworks (MOFs) represent a relatively new class of compounds that combine the advantages of inorganic compounds due to the presence of metal cations or clusters in the structure, together with almost unlimited possibilities of organic synthesis due to the use of organic ligands as linkers [1]
The use of MOFs as luminescent and electrochemical sensors, conductive materials and heterogeneous catalysts has significantly expanded the field of applications and posed new aims for the structural design of such compounds [6,7,8,9,10,11,12,13,14,15]
Using of presynthesized complexes could be essential to solve the problem of tailored synthesis

Summary

Introduction

Metal–organic frameworks (MOFs) represent a relatively new class of compounds that combine the advantages of inorganic compounds due to the presence of metal cations or clusters in the structure, together with almost unlimited possibilities of organic synthesis due to the use of organic ligands as linkers [1]. Synthesis of new porous materials with desired properties is challenging due to the many possible options for how inorganic nodes and organic linkers interact with each other and give the final structure [16]. The task becomes especially difficult if you need to combine several metals in one framework to obtain a heterometallic node [17,18]. There are five main approaches for obtaining of heterometallic MOFs described in published investigations: postsynthetic modification of MOFs by the inclusion of metal ions in the pores of the framework [21,22,23];

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Discussion

Conclusion