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Tetrazine Linkers as Plug‐and‐Play Tags for General Metal‐Organic Framework Functionalization and C<sub>60</sub> Conjugation

Belén Lerma‐Berlanga, Carolina R. Ganivet, Neyvis Almora‐Barrios, Rebecca Vismara, Jorge A. R. Navarro, Sergio Tatay, Natalia M. Padial, Carlos Martí‐Gastaldo

2022Angewandte Chemie International Edition25 citationsDOIOpen Access PDF

Abstract

The value of covalent post-synthetic modification in expanding the chemistry and pore versatility of reticular solids is well documented. Here we use mesoporous crystals of the metal-organic framework (MOF) UiO-68-TZDC to demonstrate the value of tetrazine connectors for all-purpose inverse electron-demand Diels-Alder ligation chemistry. Our results suggest a positive effect of tetrazine reticulation over its reactivity for quantitative one-step functionalization with a broad scope of alkene or alkyne dienophiles into pyridazine and dihydropyridazine frameworks. This permits generating multiple pore environments with diverse chemical functionalities and the expected accessible porosities, that is also extended to the synthesis of crystalline fulleretic materials by covalent conjugation of fullerene molecules.

Topics & Concepts

TetrazineSurface modificationBioorthogonal chemistryAlkeneCovalent bondAlkyneChemistryCombinatorial chemistryMoleculeCycloadditionMetal-organic frameworkReactivity (psychology)NanotechnologyMaterials scienceOrganic chemistryClick chemistryCatalysisPathologyAlternative medicinePhysical chemistryMedicineAdsorptionMetal-Organic Frameworks: Synthesis and ApplicationsCovalent Organic Framework ApplicationsMolecular Sensors and Ion Detection
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