Tetrazine‐Based Metal‐Organic Frameworks as Scaffolds for Post‐Synthetic Modification by the Click Reaction

Vinu, Madhan; Kulandaivel, Sivasankar; Prabu, Samikannu; Han, Jeng‐Liang; Lin, Chia Her; Yang, Chun; Demel, Jan

doi:10.1002/ejic.201901230

Cited by 20 publications

(20 citation statements)

References 42 publications

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“…Powder X-ray diffraction (PXRD) and thermal gravimetric analysis (TGA) data (see Figures S8-S11) were consistent with these new dynamic materials being isostructural with their parent MOFs PCN-57, UiO-68, and UWCM-10. Figures 1B-1D show computer generated structures (Materials Studio, 32 Forcite) viewed down the [2]rotaxane crossbar to emphasize the bulk of the 24C8 wheel and the spatial arrangement of the macrocycle with respect to the different primary linkers. A number of structural features are apparent: (1) the free volume that the 24C8 must access to transit along the axle, from one benzimidazole recognition site to the other, requires it to come close to the rotor, i.e., the central ring of the primary linker;…”

Section: Mof Synthesismentioning

confidence: 99%

Precise Spatial Arrangement and Interaction between Two Different Mobile Components in a Metal-Organic Framework

Wilson

Vojvodin

Gholami

et al. 2021

Chem

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Section: Mof Synthesismentioning

confidence: 99%

Precise Spatial Arrangement and Interaction between Two Different Mobile Components in a Metal-Organic Framework

Wilson

Vojvodin

Gholami

et al. 2021

Chem

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“…organic polymers, Metal–Organic Frameworks (MOFs)), where they have been employed as building blocks and have been shown to afford unique conducting polymers [30, 46, 48, 49] . Alternatively, they can act as scaffolds for postsynthetic modification by the click reaction to introduce bulky functional molecules into the pores of MOFs [30d,e] . Generally, s ‐tetrazines are stable and highly coloured electroactive heterocycles with a large and positive quadrupolar moment, which is why they have been widely studied as azo‐dyes and as active molecules for nonlinear optics (NLO) [31] .…”

Section: The Chemistry Of S‐tetrazinesmentioning

confidence: 99%

Enhancing Magnetic Communication between Metal Centres: The Role of s‐Tetrazine Based Radicals as Ligands

Mavragani

Kitos

Brusso

et al. 2021

Chemistry A European J

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Although 1,2,4,5‐tetrazines or s‐tetrazines have been known in the literature for more than a century, their coordination chemistry has become increasingly popular in recent years due to their unique redox activity, multiple binding sites and their various applications. The electron‐poor character of the ring and stabilization of the radical anion through all four nitrogen atoms in their metal complexes provide new aspects in molecular magnetism towards the synthesis of new high performing Single Molecule Magnets (SMMs). The scope of this review is to examine the role of s‐tetrazine radical ligands in transition metal and lanthanide based SMMs and provide a critical overview of the progress thus far in this field. As well, general synthetic routes and new insights for the preparation of s‐tetrazines are discussed, along with their redox activity and applications in various fields. Concluding remarks along with the limitations and perspectives of these ligands are discussed.

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“…14,15 These features can be also translated to MOFs for generating photoactive frameworks by reticulation of tetrazine derivatives. 16,17 Despite the poorer solubility of the tetrazine linker, the conditions optimized for TPDC only required a slight reduction of the modulator equivalents, from 40 to 10, to isolate UiO-68 TZDC as pink octahedral crystals with sizes ranging from 10 to 20 μm (Figure 1c).…”

Section: Introductionmentioning

confidence: 99%

Effect of Linker Distribution in the Photocatalytic Activity of Multivariate Mesoporous Crystals

et al. 2021

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The use of Metal-Organic Frameworks as crystalline matrices for the synthesis of multiple component or multivariate solids by the combination of different linkers into a single material has emerged as a versatile route to tailor the properties of single component phases or even access new functions. This approach is particularly relevant for Zr6-MOFs due to the synthetic flexibility of this inorganic node. However, the majority of materials is isolated as polycrystalline solids, which are not ideal to decipher the spatial arrangement of parent and exchanged linkers for the formation of homogeneous structures or heterogeneous domains across the solid. Here we use High-Throughput methodologies to optimize the synthesis of single crystals of UiO-68 and UiO-68-TZDC, a photoactive analogue based on a tetrazine dicarboxylic derivative. The analysis of the single linker phases reveals the necessity of combining both linkers to produce multivariate frameworks that combine efficient light sensitization, chemical stability and porosity, all relevant to photocatalysis. We use solvent assisted linker exchange reactions to produce a family of UiO-68-TZDC% binary frameworks, which respect the integrity and morphology of the original crystals. Our results suggest that the concentration of TZDC in solution controls the distribution of this linker in the sibling crystals for a random mixture or the formation of core-shell domains. We also demonstrate how the possibility of generating an asymmetric distribution of both linkers has a negligible effect on the electronic structure and optical bandgap of the solids but controls their performance for drastic changes in the photocatalytic activity towards proton or methyl viologen reduction.

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Tetrazine‐Based Metal‐Organic Frameworks as Scaffolds for Post‐Synthetic Modification by the Click Reaction

Cited by 20 publications

References 42 publications

Precise Spatial Arrangement and Interaction between Two Different Mobile Components in a Metal-Organic Framework

Precise Spatial Arrangement and Interaction between Two Different Mobile Components in a Metal-Organic Framework

Enhancing Magnetic Communication between Metal Centres: The Role of s‐Tetrazine Based Radicals as Ligands

Effect of Linker Distribution in the Photocatalytic Activity of Multivariate Mesoporous Crystals

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