Freezing the Nonclassical Crystal Growth of a Coordination Polymer Using Controlled Dynamic Gradients

Rubio-Martínez, Marta; Imaz, Inhar; Domingo, Neus; Abrishamkar, Afshin; Mayor, Tiago Sotto; Rossi, René M.; Carbonell, Carlos; deMello, Andrew J.; Amabilino, David B.; Maspoch, Daniel; Puigmartí‐Luis, Josep

doi:10.1002/adma.201506462

Cited by 28 publications

(31 citation statements)

References 43 publications

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“…In 2016, the same group showed that not only 1D nanoscale CP structures are generated under RD conditions, but out-of-equilibrium CP crystal structures can also be accomplished [24]. In this study, the authors show that the microfluidic synthesis (under RD conditions) of a CP constructed from Cu(II) ions and 4,4 -bipyridine linkers leads to different crystal habits.…”

Section: Continuous Flowmentioning

confidence: 72%

Continuous- versus Segmented-Flow Microfluidic Synthesis in Materials Science

Gonidec

Puigmartí‐Luis

2018

Crystals

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Materials science is a fast-evolving area that aims to uncover functional materials with ever more sophisticated properties and functions. For this to happen, new methodologies for materials synthesis, optimization, and preparation are desired. In this context, microfluidic technologies have emerged as a key enabling tool for a low-cost and fast prototyping of materials. Their ability to screen multiple reaction conditions rapidly with a small amount of reagent, together with their unique physico-chemical characteristics, have made microfluidic devices a cornerstone technology in this research field. Among the different microfluidic approaches to materials synthesis, the main contenders can be classified in two categories: continuous-flow and segmented-flow microfluidic devices. These two families of devices present very distinct characteristics, but they are often pooled together in general discussions about the field with seemingly little awareness of the major divide between them. In this perspective, we outline the parallel evolution of those two sub-fields by highlighting the key differences between both approaches, via a discussion of their main achievements. We show how continuous-flow microfluidic approaches, mimicking nature, provide very finely-tuned chemical gradients that yield highly-controlled reaction–diffusion (RD) areas, while segmented-flow microfluidic systems provide, on the contrary, very fast homogenization methods, and therefore well-defined super-saturation regimes inside arrays of micro-droplets that can be manipulated and controlled at the milliseconds scale. Those two classes of microfluidic reactors thus provide unique and complementary advantages over classical batch synthesis, with a drive towards the rational synthesis of out-of-equilibrium states for the former, and the preparation of high-quality and complex nanoparticles with narrow size distributions for the latter.

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Section: Continuous Flowmentioning

confidence: 72%

Continuous- versus Segmented-Flow Microfluidic Synthesis in Materials Science

Gonidec

Puigmartí‐Luis

2018

Crystals

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“…Accordingly, these results confirm that both Path A and Path B lead to the thermodynamically favoured CCP4 crystal form; however, the two paths are distinct and represent unique hiking routes in the free energy landscape of the system. It should also be noted that changes in the total flow rate (TFR) do not change the outcome, but simply the number of structures generated, 18 with an increase in FRR preventing the reaction from occurring (no MF-CCP-4 aggregates were observed by TEM imaging, see Methods section for further details).…”

Section: Resultsmentioning

confidence: 99%

“…As a result, no depletion of reagents occurs during self-assembly, which in turn favours a fine control over self-assembly dynamics and growth pathways (vide infra). 18 This condition, for example, has been advantageously used to isolate and study kinetically-trapped species along a single crystallization pathway. 18 Note that even though other microfluidic methods (such as droplet-based microfluidic approaches) have been used to effectively synthetize MOF crystals in a continuous and faster manner, 19 RD conditions are only allowed by microfluidic devices operating under laminar flow regimes.…”

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confidence: 99%

“…18 This condition, for example, has been advantageously used to isolate and study kinetically-trapped species along a single crystallization pathway. 18 Note that even though other microfluidic methods (such as droplet-based microfluidic approaches) have been used to effectively synthetize MOF crystals in a continuous and faster manner, 19 RD conditions are only allowed by microfluidic devices operating under laminar flow regimes. 20 Here, and in sharp contrast to previous work, 18 we show how kinetic control over the self-assembly of a functional CP, achieved under continuous-flow microfluidic conditions, unveils new and distinct kinetic pathways that are inaccessible to conventional bulk mixing experiments.…”

mentioning

confidence: 99%

“…18 Note that even though other microfluidic methods (such as droplet-based microfluidic approaches) have been used to effectively synthetize MOF crystals in a continuous and faster manner, 19 RD conditions are only allowed by microfluidic devices operating under laminar flow regimes. 20 Here, and in sharp contrast to previous work, 18 we show how kinetic control over the self-assembly of a functional CP, achieved under continuous-flow microfluidic conditions, unveils new and distinct kinetic pathways that are inaccessible to conventional bulk mixing experiments. Our approach yields unprecedented mechanistic insights into the formation of a chosen multifunctional CP and further provides the first clear example of pathway complexity in the field.…”

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confidence: 99%

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Unveiling Pathway Complexity in the Growth of a Spin-Crossover MOF via Engineered Liquid-Liquid Interfacial Reactions

Galve¹,

Abrishamkar²,

Sorrenti³

et al. 2019

Preprint

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Coordination polymers (CPs), including metal-organic frameworks (MOFs), have recently emerged as a platform to design new materials with novel applications in fields such as electronics, magnetism, catalysis, optics and gas storage/separation. However, the pathways followed and the mechanisms underlying their formation remain largely unknown and unresolved. Accordingly, the elucidation of associated growth mechanisms remains the key obstacle in accessing new properties and functions in such materials. Herein, we demonstrate that reaction-diffusion (RD) conditions accomplished within microfluidic reaction systems can be used to uncover different crystallization pathways undertaken by spin-crossover MOFs towards their thermodynamic products. Specifically, microfluidic RD mixing (providing kinetic control) enables two peculiar nucleation-growth pathways characterized by well-defined metastable intermediates, which have never been observed in bulk environments (under thermodynamic control). Contrarily, in the latter case, crystallization by particle attachment (mesoscale assembly) is observed. These unprecedented results provide a sound basis for understanding coordination polymer growth, and open up new avenues for the engineering of advanced functional materials. The chemical and physical properties of functional materials strongly depend on the nature and arrangement of their constituent units. 1 The vast current knowledge on molecular self-assembly allows for the preparation of materials with controllable physico-chemical properties, with the position and orientation of the constituent units being coordinated within the final structure. 2 In this respect, crystals of organic-inorganic materials such as coordination polymers (CPs), including metal-

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Precise Control Over Kinetics of Molecular Assembly: Production of Particles with Tunable Sizes and Crystalline Forms

Fan

Han

et al. 2020

Angewandte Chemie

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It has been long‐pursued but remains a challenge to precisely manipulate the molecular assembly process to obtain desired functional structures. Reported here is the control over the assembly of solute molecules, by a programmed recrystallization of solvent crystal grains, to form micro/nanoparticles with tunable sizes and crystalline forms. A quantitative correlation between the protocol of recrystallization temperature and the assembly kinetics results in precise control over the size of assembled particles, ranging from single‐atom catalysts, pure drug nanoparticles, to sub‐millimeter organic‐semiconductor single crystals. The extensive regulation of the assembly rates leads to the unique and powerful capability of tuning the stacking of molecules, involving the formation of single crystals of notoriously crystallization‐resistant molecules and amorphous structures of molecules with a very high propensity to crystallize, which endows it with wide‐ranging applications.

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Freezing the Nonclassical Crystal Growth of a Coordination Polymer Using Controlled Dynamic Gradients

Cited by 28 publications

References 43 publications

Continuous- versus Segmented-Flow Microfluidic Synthesis in Materials Science

Continuous- versus Segmented-Flow Microfluidic Synthesis in Materials Science

Unveiling Pathway Complexity in the Growth of a Spin-Crossover MOF via Engineered Liquid-Liquid Interfacial Reactions

Precise Control Over Kinetics of Molecular Assembly: Production of Particles with Tunable Sizes and Crystalline Forms

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