A new methanol solvate and Hirshfeld analysis of π-stacking in 2,3,6,7,10,11-hexahydroxytriphenylene solvates

The structure of 2,3,6,7,10,11-hexahydroxytriphenylene (hhtp) methanol monosolvate, C18H12O6•CH3OH, has triclinic symmetry (space group P1). The compound has a threedimensional layered network structure formed by intermolecular hydrogen bonding. Structure analysis with Hirshfeld surfaces is shown to be a sensitive method for comparing π -stacking effects in the five known solvates of hhtp. The title structure shows slightly weaker π -stacking than the dihydrate, but stronger π -stacking than the other three solvates

Layered copper-metallated covalent organic frameworks for huisgen reactions

Covalent organic frameworks (COFs) are porous materials formed through condensation reactions of organic molecules via the formation of dynamic covalent bonds. Among COFs, those based on imine and β-ketoenamine linkages offer an excellent platform for binding metallic species such as copper to design efficient heterogeneous catalysts. In this work, imine- and β-ketoenamine-based COF materials were modified with catalytic copper sites following a metallation method, which favored the formation of binding amine defects. The obtained copper-metallated COF materials were tested as heterogeneous catalysts for 1,3-dipolar cycloaddition reactions, resulting in high yields and recyclabilityThis work was supported by PID2019-106268GB-C32 and RTI2018-096138-A-I00 funded by MCIN/AEI/10.13039/ 501100011033 and EUR2020-112294 funded by MCIN/ AEI/10.13039/501100011033 and by the European Union “NextGenerationEU”/PRTR. A.E.P.-P. and F.Z. acknowledge the financial support from the Spanish Ministry of Science and Innovation, through the “María de Maeztu” Programme for Units of Excellence in R&D (CEX2018-000805-M). A.E.P.-P. acknowledges the Spanish Ministry of Science and Innovation for a Ramón y Cajal fellowship (RYC2018-024328-I). The authors acknowledge beamline P02.1 at DESY (proposal I 20190208 EC), a member of the Helmholtz Association (HGF). They thank Dr. Michael Wharmby for his assistance during the experiment at P02.1. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. I.R.-M. acknowledges an FPI-UAM 2019 fellowship from Universidad Autónoma de Madrid. P.A. acknowledges the financial support from “Ayudas para Contratos Predoctorales para la Formación de Doctores” Program of MINECO (Grant BES-2017-070838

Magnesium Exchanged Zirconium Metal−Organic Frameworks with Improved Detoxification Properties of Nerve Agents

UiO-66, MOF-808 and NU-1000 metal-organic frameworks exhibit a differentiated reactivity toward [Mg(OMe)2(MeOH)2]4 related to their pore accessibility. Microporous UiO-66 remains unchanged while mesoporous MOF-808 and hierarchical micro/mesoporous NU-1000 materials yield doped systems containing exposed MgZr5O2(OH)6 clusters in the mesoporous cavities. This modification is responsible for a remarkable enhancement of the catalytic activity toward the hydrolytic degradation of P-F and P-S bonds of toxic nerve agents, at room temperature, in unbuffered aqueous solutions

Multicomponent, Functionalized HKUST-1 Analogues Assembled via Reticulation of Prefabricated Metal-Organic Polyhedral Cavities

Metal-organic frameworks (MOFs) assembled from multiple building blocks exhibit greater chemical complexity and superior functionality in practical applications. Herein, we report a new approach based on using prefabricated cavities to design isoreticular multicomponent MOFs from a known parent MOF. We demonstrate this concept with the formation of multicomponent HKUST-1 analogues, using a prefabricated cavity that comprises a cuboctahedral Rh(II) metal-organic polyhedron functionalized with 24 carboxylic acid groups. The cavities are reticulated in three dimensions via Cu(II)-paddlewheel clusters and (functionalized) 1,3,5-benzenetricarboxylate linkers to form three- and four-component HKUST-1 analogues

Multicomponent, Functionalized HKUST‑1 Analogues Assembled via Reticulation of Prefabricated Metal–Organic Polyhedral Cavities [Dataset]

89 pages. -- PDF file includes: S1. Materials and methods; S1.1. Materials and characterization; S1.2. Experimental methods; S1.2.1. Synthesis of COOH-RhMOP, (Br)btc, (NO2)btc and (COOH)btc; S1.2.2. Stability of COOH-RhMOP under solvothermal conditions; S1.2.3. Synthesis of RhCu-btc-HKUST-1, RhCu-(Br)btc-HKUST-1, RhCu-(NO2)btc-HKUST-1, RhCu-(NH2)btc-HKUST-1 and RhCu-(COOH)btc-HKUST-1; S.1.2.4. Blank reactions for RhCu-btc-HKUST-1; S.1.2.5. Acidic disassembly of RhCu-btc-HKUST-1; S.1.2.6. Acidic digestion of RhCu-(Br)btc-HKUST-1, RhCu-(NO2)btc-HKUST-1, RhCu-(NH2)btc-HKUST-1 and RhCu-(COOH)btc-HKUST-1; S1.2.7. Study of the hydrolytic stability of RhCu-btc-HKUST-1 and Cu(II)-HKUST- 1; S1.2.8 Study of the methylene blue removal with RhCu-btc-HKUST-1 and Cu(II)-HKUST-1; S1.2.9. Study of the catalytic activity of RhCu-btc-HKUST-1 and RhCu-(COOH)btc-HKUST-1; S1.3. Computational methods; S2. Characterization of RhCu-btc-HKUST-1; S3. Characterization of Cu(II)-HKUST-1; S4. Hydrolytic stability study of RhCu-btc-HKUST-1 and Cu(II)-HKUST-1; S4.1. DFT calculations of Rh(II) and Cu(II) paddlewheels in water; S5. Characterization of RhCu-(Br)btc-HKUST-1; S6. Characterization of RhCu-(NO2)btc-HKUST-1; S7. Characterization of RhCu-(NH2)btc-HKUST-1; S8. Characterization of RhCu-(COOH)btc-HKUST-1.Metal–organic frameworks (MOFs) assembled from multiple building blocks exhibit greater chemical complexity and superior functionality in practical applications. Herein, we report a new approach based on using prefabricated cavities to design isoreticular multicomponent MOFs from a known parent MOF. We demonstrate this concept with the formation of multicomponent HKUST-1 analogues, using a prefabricated cavity that comprises a cuboctahedral Rh­(II) metal–organic polyhedron functionalized with 24 carboxylic acid groups. The cavities are reticulated in three dimensions via Cu­(II)-paddlewheel clusters and (functionalized) 1,3,5-benzenetricarboxylate linkers to form three- and four-component HKUST-1 analogues.Peer reviewe

The First One-Pot Synthesis of Metal-Organic Frameworks Functionalised with Two Transition-Metal Complexes

The synthesis of a metal-organic framework (UiO-67) functionalised simultaneously with two different transition metal complexes (Ir and Pd or Rh) through a one-pot procedure is reported for the first time. This has been achieved by an iterative modification of the synthesis parameters combined with characterisation of the resulting materials using different techniques, including X-ray absorption spectroscopy (XAS). The method also allows the first synthesis of UiO-67 with a very wide range of loadings (from 4 to 43 mol%) of an iridium complex ([IrCp*(bpydc)(Cl)Cl](2-); bpydc=2,2'-bipyridine-5,5'-dicarboxylate, Cp* = pentamethylcyclopentadienyl) through a pre-functionalisation methodology.AuthorCount:5;</p

Incorporation of photocatalytic Pt(II) complexes into imine-based layered covalent organic frameworks (COFs) through monomer truncation strategy

A new photoactive Pt (II) hydroxyquinoline complex has been covalently linked into the structure of an imine-based layered covalent organic framework (COF) through the monomer truncation strategy. Such strategy allows the incorporation of molecular fragments with only one functional group able to condensate into the imine-framework. The photocatalytic activity of the resulting Pt@COF has been applied to the oxidation of sulfides to sulfoxides, obtaining excellent results for all the studied cases, and showing that this reaction goes through both photoredox and energy transfer processes. The results obtained showed a great enhancement of the catalytic activity (up to 25,000 turnover number, TON), stability and a significant decrease on the reaction times, as a consequence of immobilization and isolation of Pt(II) centers into the organic framework. In addition, Pt@COF has been proved to be an excellent heterogeneous photocatalyst also in exclusive photoredox processes, reaching 7500 TON in hydrodebromination reactions

Incorporation of photocatalytic Pt(II) complexes into imine-based layered covalent organic frameworks (COFs) through monomer truncation strategy

A new photoactive Pt (II) hydroxyquinoline complex has been covalently linked into the structure of an imine-based layered covalent organic framework (COF) through the monomer truncation strategy. Such strategy allows the incorporation of molecular fragments with only one functional group able to condensate into the imine-framework. The photocatalytic activity of the resulting Pt@COF has been applied to the oxidation of sulfides to sulfoxides, obtaining excellent results for all the studied cases, and showing that this reaction goes through both photoredox and energy transfer processes. The results obtained showed a great enhancement of the catalytic activity (up to 25000 turnover number, TON), stability and a significant decrease on the reaction times, as a consequence of immobilization and isolation of Pt(II) centers into the organic framework. In addition, Pt@COF has been proved to be an excellent heterogeneous photocatalyst also in exclusive photoredox processes, reaching 7500 TON in hydrodebromination reactionsWe are grateful to the Spanish Government (RTI2018-095038-B-I00), “Comunidad de Madrid” and European Structural Funds (S2018/NMT-4367). A.E.P.-P. acknowledges a TALENTO grant (2017-T1/IND5148) from Comunidad de Madrid and Spanish Government (RTI2018-096138-A-I00

Functionalising metal-organic frameworks with metal complexes : the role of structural dynamics

A series of iridium-functionalised UiO-67 metal-organic frameworks (MOFs) were synthesised under conditions that simulate kinetically- and thermodynamically-controlled regimes. The degree of functionalisation depends on the reaction time and relative acidity of the native- and metallo-linkers, and can be optimised by controlling the reaction time

Revisiting Vibrational Spectroscopy to Tackle the Chemistry of Zr6O8 Metal-Organic Framework Nodes

The metal-organic framework MOF-808 contains Zr6O8nodes with a high density of vacancy sites, which can incorporate carboxylate-containing functional groups to tune chemical reactivity. Although the postsynthetic methods to modify the chemistry of the Zr6O8nodes in MOFs are well known, tackling these alterations from a structural perspective is still a challenge. We have combined infrared spectroscopy experiments and first-principles calculations to identify the presence of node vacancies accessible for chemical modifications within the MOF-808. We demonstrate the potential of our approach to assess the decoration of MOF-808 nodes with different catechol-benzoate ligands. Furthermore, we have applied advanced synchrotron characterization tools, such as pair distribution function analyses and X-ray absorption spectroscopy, to resolve the atomic structure of single metal sites incorporated into the catechol groups postsynthetically. Finally, we demonstrate the catalytic activity of these MOF-808 materials decorated with single copper sites for 1,3-dipolar cycloadditionsThis work was supported by RTI2018-096138-A-I00 funded by MCIN/AEI/10.13039/501100011033 and EUR2020- 112294 funded by MCIN/AEI/10.13039/501100011033 and by the European Union “NextGenerationEU”/PRTR. A.E.P.-P. and F.Z. acknowledge the financial support from the Spanish Ministry of Science and Innovation through the “Marí a de Maeztu” Programme for Units of Excellence in R&D (CEX2018-000805-M