Selective Implantation of Diamines for Cooperative Catalysis in Isoreticular Heterometallic Titanium–Organic Frameworks
[EN] We introduce the first example of isoreticular titanium-organic frameworks, MUV-10 and MUV-12, to show how the different affinity of hard Ti(IV) and soft Ca(II) metal sites can be used to direct selective grafting of amines. This enables the combination of Lewis acid titanium centers and available -NH, sites in two sizeable pores for cooperative cycloaddition of CO2 to epoxides at room temperature and atmospheric pressure. The selective grafting of molecules to heterometallic clusters adds up to the pool of methodologies available for controlling the positioning and distribution of chemical functions in precise positions of the framework required for definitive control of pore chemistr…
Effect of linker distribution in the photocatalytic activity of multivariate mesoporous crystals
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 methodologi…
Innentitelbild: Selective Implantation of Diamines for Cooperative Catalysis in Isoreticular Heterometallic Titanium–Organic Frameworks (Angew. Chem. 21/2021)
Inside Cover: Selective Implantation of Diamines for Cooperative Catalysis in Isoreticular Heterometallic Titanium–Organic Frameworks (Angew. Chem. Int. Ed. 21/2021)
Tetrazine Linkers as Plug-and-Play Tags for General Framework Functionalization and C60 Conjugation
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 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 synthe…
Wrapping up Metal-Organic Framework Crystals with Carbon Nanotubes
The presence of tetrazine units in the organic nodes of UiO- 68-TZCD controls the formation of ultrathin coatings of single wall nanotubes that decorate the surface of the crystal. These crystal hybrids can be prepared straightforwardly in one step and are extraordinarily respectful with the properties of the framework for combination of mesoporosity and surface areas near 4.000 m·g-1 ,with excellent stability in water, and conductivities at room temperature of 4·10-2 S·cm-1 even at very low carbon weight contents (2.3 wt%).
Influence of Peripheral Substitution on the Magnetic Behavior of Single-Ion Magnets Based on Homo- and Heteroleptic TbIIIBis(phthalocyaninate)
A series of homoleptic ([Tb(III)(Pc)(2) ]) and heteroleptic ([Tb(III)(Pc)(Pc')]) Tb(III) bis(phthalocyaninate) complexes that contain different peripheral substitution patterns (i.e., tert-butyl or tert-butylphenoxy groups) have been synthesized in their neutral radical forms and then reduced into their corresponding anionic forms as stable tetramethylammonium/tetrabutylammonium salts. All of these compounds were spectroscopically characterized and their magnetic susceptibility properties were investigated. As a general trend, the radical forms exhibited larger energy barriers for spin reversal than their corresponding reduced compounds. Remarkably, heteroleptic complexes that contain elect…
Tetrazine Linkers as Plug‐and‐Play Tags for General Metal‐Organic Framework Functionalization and C 60 Conjugation
Permanent Porosity in Hydroxamate Titanium-Organic Polyhedra.
Following the synthesis of hydroxamate titanium–organic frameworks, we now extend these siderophore-type linkers to the assembly of the first titanium–organic polyhedra displaying permanent porosity. Mixed-linker versions of this molecular cage (cMUV-11) are also used to demonstrate the effect of pore chemistry in accessing high surface areas of near 1200 m2·g–1.
Direct Visualization of Pyrrole Reactivity upon Confinement within a Cyclodextrin Metal–Organic Framework
Metal–organic frameworks can be used as porous templates to exert control over polymerization reactions. Shown here are the possibilities offered by these crystalline, porous nanoreactors to capture highly-reactive intermediates for a better understanding of the mechanism of polymerization reactions. By using a cyclodextrin framework the polymerization of pyrrole is restricted, capturing the formation of terpyrrole cationic intermediates. Single-crystal X-ray diffraction is used to provide definite information on the supramolecular interactions that induce the formation and stabilization of a conductive array of cationic complexes.
Direct visualization of pyrrole reactivity by confined oxidation in a Cyclodextrin Metal‐Organic Framework
Metal-organic frameworks can be used as porous templates to exert control over polymerization reactions. Shown here are the possibilities offered by these crystalline, porous nanoreactors to capture highly‐reactive intermediates for a better understanding of the mechanism of polymerization reactions. By using a cyclodextrin framework the polymerization of pyrrole is restricted, capturing the formation of terpyrrole cationic intermediates. Single‐crystal X‐ray diffraction is used to provide definite information on the supramolecular interactions that induce the formation and stabilization of a conductive array of cationic complexes.
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