Preparation, optimization and evolution of the kinetic mechanism of an Fe-MIL-88A metal–organic framework

Bagherzadeh, Elham; Zebarjad, Seyed Mojtaba; Hosseini, Hamid Reza Madaah; Chagnon, P.

doi:10.1039/c8ce01876f

Cited by 28 publications

(14 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…35 Using both coordination modulation, the addition of monotopic modulators that mimic the organic ligands, and oxidation modulation, utilising metal starting materials in different oxidation states to those in the product, it is possible to exert kinetic control over self-assembly and select either the non-interpenetrated MIL-88D(Fe) kinetic product or the two-fold interpenetrated MIL-126(Fe) polymorph that is the thermodynamic product. 34 Coordination modulation has also been used to control the physical properties of Fe-MOFs, such as particle morphology [36][37][38] and size. 39,40 Herein, we apply coordination and oxidation modulation to the synthesis of Fe-terephthalate MOFs, a much more complex system, allowing mapping of the phase space and simple, reproducible isolation of individual phases.…”

Section: Introductionmentioning

confidence: 99%

Exploring and expanding the Fe-terephthalate metal–organic framework phase space by coordination and oxidation modulation

et al. 2021

View full text Add to dashboard Cite

show abstract

Section: Introductionmentioning

confidence: 99%

Exploring and expanding the Fe-terephthalate metal–organic framework phase space by coordination and oxidation modulation

et al. 2021

View full text Add to dashboard Cite

show abstract

“…35 Using both coordination modulation, the addition of monotopic modulators that mimic the organic ligands, and oxidation modulation, utilising metal starting materials in different oxidation states to those in the product, it is possible to exert kinetic control over self-assembly and select either the non-interpenetrated MIL-88D(Fe) kinetic product or the twofold interpenetrated MIL-126(Fe) polymorph that is the thermodynamic product. 34 Coordination modulation has also been used to control the physical properties of Fe-MOFs, such as particle morphology [36][37][38] and size. 39,40 Herein, we apply coordination and oxidation modulation to the synthesis of Fe-terephthalate MOFs, a much more complex system, allowing mapping of the phase space and simple, reproducible isolation of individual phases.…”

Section: Introductionmentioning

confidence: 99%

Exploring and Expanding the Fe-Terephthalate Metal-Organic Framework Phase Space by Coordination and Oxidation Modulation

Bara

Meekel

Pakamorė

et al. 2021

Preprint

View full text Add to dashboard Cite

The synthesis of phase pure metal-organic frameworks (MOFs) – network solids of metal clusters connected by organic linkers – is often complicated by the possibility of forming multiple diverse phases from one metal-ligand combination. For example, there are at least six Fe-terephthalate MOFs reported to date, with many examples of erroneous assignment of phase based on diffraction data alone. Herein, we show that modulated self-assembly can be used to influence the kinetics of self-assembly of Fe-terephthalate MOFs. We comprehensively assess the effect of addition of both coordinating modulators and pH modulators to the outcome of syntheses, as well as probing the influence of the oxidation state of the Fe precursor (oxidation modulation) and the role of the counteranion on the phase(s) formed. In doing so, we shed light on the thermodynamic landscape of this phase system, uncover mechanistics of modulation, provide robust routes to phase pure materials, often as single crystals, and introduce two new Fe-terephthalate MOFs to an already complex system. The results highlight the potential of modulated self-assembly to bring precision control and new structural diversity to systems that have already received significant study.

show abstract

“…To date, synthesis protocols of monodisperse iron(III) fumarate particles are not well established . Advances that were made to characterize the crystallization of this structure either rely on the usage of modulating additives or fail to characterize the particles’ functionality and biocompatibility. ,,− Mastering the synthesis of iron(III) fumarate particles and understanding the relationship between their morphology, structure, and material and biological properties are imperative to unlocking their potential for biomedical purposes. The study presented here therefore serves multiple purposes: ( i ) to systematically study the relationship between synthesis conditions (e.g., heat source, reaction parameters, solvent, reactant concentration) and the morphology and crystallinity of iron(III) fumarate particles produced; ( ii ) to investigate the impact of morphology on the particles’ intrinsic material properties (e.g., MRI activity and porosity); and ( iii ) to explore their biocompatibility and connect those data with the physicochemical parameters (e.g., morphology and size), see Figure .…”

Section: Introductionmentioning

confidence: 99%

Tuning the Morphological Appearance of Iron(III) Fumarate: Impact on Material Characteristics and Biocompatibility

Hirschle

Böll

et al. 2020

Chem. Mater.

View full text Add to dashboard Cite

Iron(III) fumarate materials are well suited for biomedical applications as they feature biocompatible building blocks, porosity, chemical functionalizability, and magnetic resonance imaging (MRI) activity. The synthesis of these materials however is difficult to control and it has been challenging to produce monodisperse particle sizes and morphologies that are required in medical use. Here, we report the optimization of iron(III) fumarate nano and microparticles synthesis by surfactant-free methods, including room temperature, solvothermal, microwave, and microfluidic conditions. Four variants of iron(III) fumarate with distinct morphologies were isolated and are characterized in detail. Structural characterization shows that all iron(III) fumarate variants exhibit the metal-organic framework (MOF) structure of MIL-88A. Nanoparticles with a diameter of 50 nm were produced, which contain crystalline areas not exceeding 5 nm. Solvent-dependent swelling of the crystalline particles was monitored using in-situ X-ray diffraction. Cytotoxicity experiments showed that all iron(III) fumarate variants feature adequate bio-tolerability and no distinct interference with cellular metabolism at low concentrations. Magnetic resonance relaxivity studies using clinical MRI equipment, on the other hand, proved that the MRI contrast characteristics depend on particle size and morphology. All in all, this study demonstrates the possibility of tuning the morphological appearance of iron(III) fumarate particles and illustrates the importance of optimizing synthesis conditions for the development of new biomedical materials.

show abstract

Preparation, optimization and evolution of the kinetic mechanism of an Fe-MIL-88A metal–organic framework

Abstract: Investigating the kinetics of crystallization, growth behavior and morphological changes through statistical studies of Fe-MIL-88A suggested an autocatalytic nucleation mechanism.

Cited by 28 publications

References 27 publications

Exploring and expanding the Fe-terephthalate metal–organic framework phase space by coordination and oxidation modulation

Exploring and expanding the Fe-terephthalate metal–organic framework phase space by coordination and oxidation modulation

Exploring and Expanding the Fe-Terephthalate Metal-Organic Framework Phase Space by Coordination and Oxidation Modulation

Tuning the Morphological Appearance of Iron(III) Fumarate: Impact on Material Characteristics and Biocompatibility

Contact Info

Product

Resources

About