753031-26-4Relevant articles and documents
Effect of Linker Distribution in the Photocatalytic Activity of Multivariate Mesoporous Crystals
Lerma-Berlanga, Belén,R. Ganivet, Carolina,Almora-Barrios, Neyvis,Tatay, Sergio,Peng, Yong,Albero, Josep,Fabelo, Oscar,González-Platas, Javier,García, Hermenegildo,M. Padial, Natalia,Martí-Gastaldo, Carlos
supporting information, p. 1798 - 1806 (2021/02/01)
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 are 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 and the reaction time control the distribution of this linker in the sibling crystals for a uniform 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 band gap of the solids but controls their performance for drastic changes in the photocatalytic activity toward proton or methyl viologen reduction.
Tetrazine-Based Metal-Organic Frameworks as Scaffolds for Post-Synthetic Modification by the Click Reaction
Demel, Jan,Han, Jeng-Liang,Lin, Chia-Her,Prabu, Samikannu,Sivasankar, Kulandaivel,Vinu, Madhan,Yang, Chun-Chuen
supporting information, p. 461 - 466 (2020/02/04)
Metal-organic frameworks are one of the most active research fields today. Despite the progress in recent years, synthesis of highly porous structures bearing functional groups for specific applications remains a challenge. Here, we describe synthesis of Zr(IV) and Hf(IV)-based tetrazine containing metal-organic frameworks, ZrTz-68 and HfTz-68 with pore size of 2.1 nm, specific surface area up to 4217 m2 g–1, and a UiO-68 topology. The synthesis can be done on a multi-gram scale from inexpensive linker 4,4'-(1,2,4,5-tetrazine-3,6-diyl)dibenzoic acid (H2TzDB). Moreover, because of the π-conjugated tetrazine groups these MOFs can be easily post-synthetically modified by a “click” reaction maintaining the crystallinity of the framework. Due to the diversity of “clickable” substituents, this strategy represents highly versatile tool for a wide range of applications.
Clicking 1,2,4,5-tetrazine and cyclooctynes with tunable reaction rates
Chen, Weixuan,Wang, Danzhu,Dai, Chaofeng,Hamelberg, Donald,Wang, Binghe
supporting information; experimental part, p. 1736 - 1738 (2012/03/09)
Substituted tetrazines have been found to undergo facile inverse electron demand Diels-Alder reactions with "tunable" reaction rates.
