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

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

Versatile Barium and Calcium Imidazolium-Dicarboxylate Heterogeneous Catalysts in Quinoline Synthesis

This article details the development of heterogeneous catalysts based on calcium and barium in combination with the organic linker 1,3-bis(carboxymethyl)imidazolium (bcmim). The linker and the materials from alkaline earth metals are easily prepared under very smooth conditions. The use of linkers with different counterions (Cl or Br) provided different materials. Calcium- and barium-based catalysts were successfully employed in the preparation of quinoline derivatives from ketones and 2-aminoarylaldehydes or 2-aminoarylketones. In general, barium-based catalysts provided better results than calcium, although the latter are an excellent complement for certain substrates. Thus, a notable feature of such catalysts is the possibility of accessing a variety of complementary heterogeneous catalytic systems, rendering the catalysis adaptive to the reactant.The Ministerio de Economía y Competitividad, CTQ2015-66624-P) and the University of Alicante (VIGROB-285) are gratefully acknowledged for financial support. M. A. S. thanks the Ministerio de Educación, Cultura y Deporte, FPU15/06040) for a predoctoral fellowship

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

New Alkaline-Earth Polymeric Frameworks as green materials for sorption and heterogeneous catalysis

Metal-Organic Frameworks (or MOFs) are porous organic-inorganic crystalline materials in which the metallic centers are joined through organic ligands via coordination bonds to give frameworks with different dimensionalities. The work presented in this thesis is focused on the obtaining of new MOFs using alkaline-earth elements as metal centers, which could represent a comparatively cheap, nontoxic and green alternative to conventional MOFs based on transition metals or rare-earth elements.The obtained materials have shown interesting properties like heterogeneous catalysis under mild conditions or selective sorption of organic compounds.Peer reviewe