Bottom-up approach for the preparation of hybrid nanosheets based on coordination polymers made of metal–diethyloxaloacetate complexes linked by 4,4′-bipyridine

Portolés‐Gil, Núria; Parra-Aliana, Ricard; Álvarez‐Larena, Ángel; Domingo, Concepción; Ayllón, José A.; López‐Periago, Ana M.

doi:10.1039/c7ce00909g

Cited by 6 publications

(3 citation statements)

References 33 publications

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“…For hybrid coordination polymers, several examples of this morphology have already been observed in samples obtained by solvothermal , and supercritical crystallization techniques. The recovered sample at 20 h was mainly crystalline (Figure b).…”

Section: Resultsmentioning

confidence: 81%

Crystalline Curcumin bioMOF Obtained by Precipitation in Supercritical CO₂ and Structural Determination by Electron Diffraction Tomography

Portolés‐Gil

Lanza

Aliaga‐Alcalde

et al. 2018

ACS Sustainable Chem. Eng.

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This article analyzes the use of supercritical CO 2 green technology in the reactive crystallization processes involved in the formation of a bioMOF that contains curcumin and Zn II metal centers. A new phase with a [Zn(curcumin)] n composition, termed sc-CCMOF-1, is presented. The developed scCO 2 protocol allows high yields of the small-sized crystalline material, which was characterized by the use of the recently developed electron diffraction tomography method applied to the resolution of submicrometric crystals. A remarkable 3D macrostructure with a complex morphology was obtained. To analyze the crystallization mechanism, multiple identical runs were performed under similar experimental conditions to study in each time period the crystal growth progress ex situ by X-ray diffraction and scanning electron microscopy. These experiments indicated that the process to achieve the sc-CCMOF-1 in a crystalline form involves the formation of amorphous or semicrystalline metastable phases that derived into hierarchical stable and crystalline nanoflower aggregates. In addition, a potential therapeutic application of the bioMOF has been tested by studying the released of the curcumin molecule at neutral pH.

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Section: Resultsmentioning

confidence: 81%

Crystalline Curcumin bioMOF Obtained by Precipitation in Supercritical CO₂ and Structural Determination by Electron Diffraction Tomography

Portolés‐Gil

Lanza

Aliaga‐Alcalde

et al. 2018

ACS Sustainable Chem. Eng.

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“…scCO 2 has been traditionally used for removing entrapped solvents within MOF structures. However, in the past few years, it has also been used in our research group as a solvent for the synthesis of MOFs, either by using exclusively scCO 2 , − or adding a cosolvent, with interesting applications in medicine (bioMOFs), sensors or gas adsorption after hybridizing with graphene aerogels . In essence, the use of the scCO 2 technology has proved excellent to prepare materials for biomedical applications .…”

Section: Introductionmentioning

confidence: 99%

Supercritical CO₂ Synthesis of Porous Metalloporphyrin Frameworks: Application in Photodynamic Therapy

et al. 2023

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A series of porous metalloporphyrin frameworks prepared from the 5,10,15,20-tetra(4-pyridyl)porphyrin (H 2 TPyP) linker and four metal complexes, M(hfac) 2 M = Cu(II), Zn(II), Co(II), and Ni(II) (hfac: 1,1,1,5,5,5-hexafluoroacetylacetonate), were obtained using supercritical CO 2 (scCO 2 ) as a solvent. All the materials, named generically as [M-TPyP] n , formed porous metal− organic frameworks (MOFs), with surface areas of ∼450 m 2 g −1 . All MOFs were formed through the coordination of the metal to the exocyclic pyridine moieties in the porphyrin linker. For Cu(II), Zn(II), and Co(II), incomplete metal coordination of the inner pyrrole ring throughout the structure was observed, giving place to MOFs with substitutional defects and leading to a certain level of disorder and limited crystallinity. These samples, prepared using scCO 2 , were precipitated as nano-to micrometric powders. Separately, a layering technique from a mixture of organic solvents was used to crystallize high-quality crystals of the Co(II) based MOF, obtained with the formula [{Co(hfac) 2 } 2 H 2 TPyP] n . The crystal structure of this MOF was elucidated by single-crystal synchrotron X-ray diffraction. The Zn(II)-based MOF was selected as a potential photodynamic therapy drug in the SKBR-3 tumoral cell line showing outstanding performance. This MOF resulted to be nontoxic, but after 15 min of irradiation at 630 nm, using either 1 or 5 μM concentration of the product, almost 70% of tumor cells died after 72 h.

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“…This axiom is applied in this work, since the designed synthetic processes avoid the use of solvothermal techniques and high-boiling-point solvents. Previous publications had shown that a series of bipyridyl CPs can be easily prepared by using greener techniques. − …”

Section: Introductionmentioning

confidence: 99%

Tuning the Structure and Flexibility of Coordination Polymers via Solvent Control of Tritopic Triazine Conformation during Crystallization

Portolés‐Gil

López‐Periago

Borrás

et al. 2020

Crystal Growth & Design

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Soft crystallization routes for the controlled growth of one- and two-dimensional Cu(II)-coordination polymers of the type [(Cu(hfa)2) x (3-tpt)] n (hfa = hexafluoroacetylacetonate, 3-tpt = 2,4,6-tris(3-pyridyl)-1,3,5-triazine) are described. Three volatile solvents with different protic/aprotic characteristics were chosen as the reaction media, e.g., supercritical CO2, chloroform, and ethanol. Five (1–5) new compounds were crystallized, with different structures and Cu(II)/3-tpt ratios. The structures of 3-tpt and five new coordination polymers were elucidated by single-crystal synchrotron X-ray diffraction. A description of the crystallization pathways followed for the synthesis of the individual compounds is given based on the protic or aprotic character of the used solvents and reagents’ solubility constraints. The main novelty of the work relies in establishing the foundations of 3-tpt isomeric control during crystallization through solvent selection. From the five precipitated new compounds, 3 displays a significant framework flexibility, associated with N2 adsorption at low temperature, presenting a stepwise adsorption isotherm. The N2 adsorption process was followed by in situ synchrotron X-ray powder diffraction.

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Bottom-up approach for the preparation of hybrid nanosheets based on coordination polymers made of metal–diethyloxaloacetate complexes linked by 4,4′-bipyridine

Abstract: [M(deox)2(bpy)]∞ precipitated as nanosheets arranged in different morphologies.

Cited by 6 publications

References 33 publications

Crystalline Curcumin bioMOF Obtained by Precipitation in Supercritical CO₂ and Structural Determination by Electron Diffraction Tomography

Crystalline Curcumin bioMOF Obtained by Precipitation in Supercritical CO₂ and Structural Determination by Electron Diffraction Tomography

Supercritical CO₂ Synthesis of Porous Metalloporphyrin Frameworks: Application in Photodynamic Therapy

Tuning the Structure and Flexibility of Coordination Polymers via Solvent Control of Tritopic Triazine Conformation during Crystallization

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Bottom-up approach for the preparation of hybrid nanosheets based on coordination polymers made of metal–diethyloxaloacetate complexes linked by 4,4′-bipyridine

Abstract: [M(deox)2(bpy)]∞ precipitated as nanosheets arranged in different morphologies.

Cited by 6 publications

References 33 publications

Crystalline Curcumin bioMOF Obtained by Precipitation in Supercritical CO2 and Structural Determination by Electron Diffraction Tomography

Crystalline Curcumin bioMOF Obtained by Precipitation in Supercritical CO2 and Structural Determination by Electron Diffraction Tomography

Supercritical CO2 Synthesis of Porous Metalloporphyrin Frameworks: Application in Photodynamic Therapy

Tuning the Structure and Flexibility of Coordination Polymers via Solvent Control of Tritopic Triazine Conformation during Crystallization

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Product

Resources

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Crystalline Curcumin bioMOF Obtained by Precipitation in Supercritical CO₂ and Structural Determination by Electron Diffraction Tomography

Crystalline Curcumin bioMOF Obtained by Precipitation in Supercritical CO₂ and Structural Determination by Electron Diffraction Tomography

Supercritical CO₂ Synthesis of Porous Metalloporphyrin Frameworks: Application in Photodynamic Therapy