De novo synthesis of mesoporous photoactive titanium(IV)-organic frameworks with MIL-100 topology

[EN] Most developments in the chemistry and applications of metal-organic frameworks (MOFs) have been made possible thanks to the value of reticular chemistry in guiding the unlimited combination of organic connectors and secondary building units (SBUs) into targeted architectures. However, the development of new titanium-frameworks still remains limited by the difficulties in controlling the formation of persistent Ti-SBUs with predetermined directionality amenable to the isoreticular approach. Here we report the synthesis of a mesoporous Ti-MOF displaying a MIL-100 topology. MIL-100(Ti) combines excellent chemical stability and mesoporosity, intrinsic to this archetypical family of porous…

Linker depletion for missing cluster defects in non-UiO Metal-Organic Frameworks

Defect engineering is a valuable tool to tune the properties of metal–organic frameworks. However, defect chemistry remains still predominantly limited to UiO-type MOFs. We describe the preferential formation of missing cluster defects in heterometallic titanium–organic frameworks of the MUV-10 family when synthesised in sub-stoichiometric linker conditions. Our results show the value of integrating experimental work, computational modelling and thorough characterization in rationalizing the impact of defects over the porosity and structure of this family of materials. Correlation of experiment with computational models reveals the dominance of missing cluster vacancies in the pore size dis…

Diffusion Control in Single-Site Zinc Reticular Amination Catalysts.

Zn-containing metal-organic frameworks have been used for the first time as heterogeneous catalysts in the amination of C-Cl bonds. The use of extended bis(pyrazolate) linkers can generate highly porous architectures, which favor the diffusion of amines to the confined spaces with respect to other imidazolate frameworks with narrower pore windows. The N4Zn nodes of the Zn-reticular framework show comparable activity to state-of-the-art homogeneous Zn amination catalysts, avoiding the use of basic conditions, precious metals, or other additives. This is combined with long-term activity and stability upon several reaction cycles, without contamination of the reaction product. ispartof: INORGA…

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…

Effect of modulator connectivity on promoting defectivity in titanium–organic frameworks

The recognition of defect chemistry as a true synthetic tool for targeted creation of defects and controllable performance remains limited by the pool of frameworks explored. The value of defect engineering in controlling the properties of defective frameworks has been beautifully exemplified and largely demonstrated with UiO-type materials based on Zr(iv) nodes. However, titanium–organic frameworks remain largely unexplored in this context arguably due to the complex chemistry in solution of Ti(iv) and the difficulties in growing crystalline solids. We report a systematic study on the ability of mono- and dicarboxylic modulators (benzoic and isophthalic acid) to promote defect creation in …

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)

Heterometallic Titanium–Organic Frameworks by Metal-Induced Dynamic Topological Transformations

Reticular chemistry has boosted the design of thousands of metal and covalent organic frameworks for unlimited chemical compositions, structures, and sizable porosities. The ability to generate porous materials at will on the basis of geometrical design concepts is responsible for the rapid growth of the field and the increasing number of applications derived. Despite their promising features, the synthesis of targeted homo- and heterometallic titanium–organic frameworks amenable to these principles is relentlessly limited by the high reactivity of this metal in solution that impedes the controlled assembly of titanium molecular clusters. We describe an unprecedented methodology for the syn…

Heterometallic Titanium-Organic Frameworks as Dual Metal Catalysts for Synergistic Non-Buffered Hydrolysis of Nerve Agent Simulants

Heterometallic metal-organic frameworks (MOFs) can offer important advantages over their homometallic counterparts to enable targeted modification of their adsorption, structural response, electronic structure, or chemical reactivity. However, controlling metal distribution in these solids still remains a challenge. The family of mesoporous titanium-organic frameworks, MUV-101(M), displays heterometallic TiM2 nodes assembled from direct reaction of Ti(IV) and M(II) salts. We use the degradation of nerve agent simulants to demonstrate that only TiFe2 nodes are capable of catalytic degradation in non-buffered conditions. By using an integrative experimental-computational approach, we rational…

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…

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

Crystalline supramolecular organic frameworksviahydrogen-bonding between nucleobases

We report a crystalline supramolecular framework assembled by H-bonding interactions between covalently fused monomers equipped with two guanine-cytosine nucleobase pairs.

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.

Catalytic activity of a CuGHK peptide-based porous material

The CuGHK peptide-based porous material with a periodic distribution of pockets decorated with lysine side chain active sites was synthesized using a room temperature one-step method and used as a heterogeneous organocatalyst. The pockets are capable of benzaldehyde molecule uptake and show high activity in the Henry reaction with nitromethane. Mechanistic pathways are investigated using an integrative experimental/computational approach.

Translocation of enzymes into a mesoporous MOF for enhanced catalytic activity under extreme conditions

Translocation of protease into mesoporous MIL-101-NH2 results in enhanced catalytic activity, excellent recyclability and tolerance to competing enzymes.

Homochiral Metal-Organic Frameworks for Enantioselective Separations in Liquid Chromatography

Selective separation of enantiomers is a substantial challenge for the pharmaceutical industry. Chromatography on chiral stationary phases is the standard method, but at a very high cost for industrial-scale purification due to the high cost of the chiral stationary phases. Typically, these materials are poorly robust, expensive to manufacture, and often too specific for a single desired substrate, lacking desirable versatility across different chiral analytes. Here, we disclose a porous, robust homochiral metal–organic framework (MOF), TAMOF-1, built from copper(II) and an affordable linker prepared from natural l-histidine. TAMOF-1 has shown to be able to separate a variety of model…

Chemical Engineering of Photoactivity in Heterometallic Titanium–Organic Frameworks by Metal Doping

[EN] We report a new family of titanium-organic frameworks that enlarges the limited number of crystalline, porous materials available for this metal. They are chemically robust and can be prepared as single crystals at multi-gram scale from multiple precursors. Their heterometallic structure enables engineering of their photoactivity by metal doping rather than by linker functionalization. Compared to other methodologies based on the post-synthetic metallation of MOFs, our approach is well-fitted for controlling the positioning of dopants at an atomic level to gain more precise control over the band-gap and electronic properties of the porous solid. Changes in the band-gap are also rationa…

Origin of the Chemiresistive Response of Ultrathin Films of Conductive Metal–Organic Frameworks

Conductive metal-organic frameworks are opening new perspectives for the use of these porous materials for applications traditionally limited to more classical inorganic materials, such as their integration into electronic devices. This has enabled the development of chemiresistive sensors capable of transducing the presence of specific guests into an electrical response with good selectivity and sensitivity. By combining experimental data with computational modelling, a possible origin for the underlying mechanism of this phenomenon in ultrathin films (ca. 30 nm) of Cu-CAT-1 is described. ispartof: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION vol:57 issue:46 pages:15086-15090 ispartof: location…

Bottom‐Up Fabrication of Semiconductive Metal-Organic Framework Ultrathin Films

Though generally considered insulating, recent progress on the discovery of conductive porous metal-organic frameworks (MOFs) offers new opportunities for their integration as electroactive components in electronic devices. Compared to classical semiconductors, these metal-organic hybrids combine the crystallinity of inorganic materials with easier chemical functionalization and processability. Still, future development depends on the ability to produce high-quality films with fine control over their orientation, crystallinity, homogeneity, and thickness. Here self-assembled monolayer substrate modification and bottom-up techniques are used to produce preferentially oriented, ultrathin, con…

Hydroxamate Titanium–Organic Frameworks and the Effect of Siderophore-Type Linkers over Their Photocatalytic Activity

The chemistry of metal–organic frameworks (MOFs) relies on the controlled linking of organic molecules and inorganic secondary building units to assemble an unlimited number of reticular frameworks. However, the design of porous solids with chemical stability still remains limited to carboxylate or azolate groups. There is a timely opportunity to develop new synthetic platforms that make use of unexplored metal binding groups to produce metal–linker joints with hydrolytic stability. Living organisms use siderophores (iron carriers in Greek) to effectively assimilate iron in soluble form. These compounds make use of hard oxo donors as hydroxamate or catecholate groups to coordinate metal Lew…

CCDC 2106824: Experimental Crystal Structure Determination

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CCDC 1898811: Experimental Crystal Structure Determination

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CCDC 2106822: Experimental Crystal Structure Determination

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CCDC 1898971: Experimental Crystal Structure Determination

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CCDC 1960226: Experimental Crystal Structure Determination

Related Article: Javier Castells-Gil, Natalia M. Padial, Neyvis Almora-Barrios, Rodrigo Gil-San-Millán, María Romero-Ángel, Virginia Torres, Iván da Silva, Bruno C.J. Vieira, Joao C. Waerenborgh, Jaciek Jagiello, Jorge A.R. Navarro, Sergio Tatay, Carlos Martí-Gastaldo|2020|Cell Press: Chem|6|3118|doi:10.1016/j.chempr.2020.09.002

CCDC 1884457: Experimental Crystal Structure Determination

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CCDC 1965235: Experimental Crystal Structure Determination

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CCDC 2023345: Experimental Crystal Structure Determination

Related Article: Belén Lerma-Berlanga, Carolina R. Ganivet, Neyvis Almora-Barrios, Sergio Tatay, Yong Peng, Josep Albero, Oscar Fabelo, Javier González-Platas, Hermenegildo García, Natalia M. Padial, Carlos Martí-Gastaldo|2021|J.Am.Chem.Soc.|143|1798|doi:10.1021/jacs.0c09015

CCDC 1898969: Experimental Crystal Structure Determination

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CCDC 2106823: Experimental Crystal Structure Determination

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CCDC 1898970: Experimental Crystal Structure Determination

Related Article: M. Nieves Corella-Ochoa, Jesús B. Tapia, Heather N. Rubin, Vanesa Lillo, Jesús González-Cobos, José Luis Núñez-Rico, Salvador R.G. Balestra, Neyvis Almora-Barrios, Marina Lledós, Arnau Güell-Bara, Juanjo Cabezas-Giménez, Eduardo C. Escudero-Adán, Anton Vidal-Ferran, Sofía Calero, Melissa Reynolds, Carlos Martí-Gastaldo, José Ramón Galán-Mascarós|2019|J.Am.Chem.Soc.|141|14306|doi:10.1021/jacs.9b06500

CCDC 2023346: Experimental Crystal Structure Determination

Related Article: Bel��n Lerma-Berlanga, Carolina R. Ganivet, Neyvis Almora-Barrios, Sergio Tatay, Yong Peng, Josep Albero, Oscar Fabelo, Javier Gonz��lez-Platas, Hermenegildo Garc��a, Natalia M. Padial, Carlos Mart��-Gastaldo|2021|J.Am.Chem.Soc.|143|1798|doi:10.1021/jacs.0c09015

CCDC 1871195: Experimental Crystal Structure Determination

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