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. 2019 Sep 25;24(19):3480.
doi: 10.3390/molecules24193480.

Substituted 1,3,5-Triazine Hexacarboxylates as Potential Linkers for MOFs

Arne Klinkebiel  1 , Ole Beyer  2 , Ulrich Lüning  3
Affiliations

Substituted 1,3,5-Triazine Hexacarboxylates as Potential Linkers for MOFs

Arne Klinkebiel et al. Molecules. .

Abstract

Hexacarboxylates are promising linkers for MOFs such as NU-109 or NU-110, which possess large values for surfaces and pore volumina. Starting from 2,4,6-tris(bromoaryl)-1,3,5-triazines, palladium-catalyzed cross coupling reactions (Suzuki-Miyaura, Sonogashira-Hagihara) form elongated hexacarboxylate linkers. Eight new 2,4,6-tris(biphenyl) and 2,4,6-tris(phenylethynylphenyl) 1,3,5-triazines have been prepared in quantities ranging from 40 mg to 1.1 g. In five cases, one of the arms of the linker carries an additional functionality (NO2 or OMe).

Keywords: Sonogashira reaction; Suzuki reaction; ligands; metal organic framework; triazine.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Tridentate mono-substituted triazine based linkers 1 and 2 [13,14]. The elongated tricarboxylic acids 2 were synthesized from the respective tribromides 3a–c using Suzuki-Miyaura couplings.
Figure 2
Figure 2
Necessary isophthalates 4 and 5 for the palladium catalyzed cross-coupling reactions to form hexadentate linkers 6 and 8.
Figure 3
Figure 3
Syntheses of hexadentate mono-substituted triazine based linkers 6 and 7: a) in dioxane/water (10:1): Pd(dppf)Cl2, KOAc (6a, 88%), Pd(PPh3)4, K3PO4 (6b, 83%; 6c, 81%). b) LiOH, H2O (7a, quant.; 7b, quant.; 7c, 89%).
Figure 4
Figure 4
Syntheses of hexadentate mono-substituted alkyne containing triazine based linkers 11: a) Pd(PPh3)4, CuI, NEt3 (9a: 75%; 9b: 72%; 9c: 94%); b) K2CO3, MeOH (10a, 10c: quant.); c) Pd(PPh3)2Cl2, CuI, NEt3 (11a: 79%; 11c: 81%).
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