Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 29, Pages 15920-15927Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202101611
Keywords
crystallization; metal– organic frameworks; microfluidic technologies; pathway complexity; reaction-diffusion conditions
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Funding
- European Union (ERC-2015-STG microCrysFact) [677020]
- European Union (ERC-2016-CoG) [724681-S-CAGE]
- Swiss National Science Foundation [200021_181988]
- Spanish MINECO (Unit of Excellence Maria de Maeztu) [MDM-2015-0538, CTQ2017-89528-P]
- Generalitat Valenciana [PROMETEU/2019/066, PROMETEO/2017/066]
- MINECO
- Generalitat Valenciana
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By achieving diffusion-controlled mixing of reagents at the very early stages of crystallization process using continuous-flow microfluidic devices, two distinct nucleation-growth pathways of a spin-crossover MOF towards its thermodynamic product were observed. Additionally, full-atom molecular dynamics simulations confirmed the occurrence of these pathways during crystal growth. In contrast, crystallization by particle attachment was observed under turbulent mixing conditions.
Coordination polymers (CPs), including metal-organic frameworks (MOFs), are crystalline materials with promising applications in electronics, magnetism, catalysis, and gas storage/separation. However, the mechanisms and pathways underlying their formation remain largely undisclosed. Herein, we demonstrate that diffusion-controlled mixing of reagents at the very early stages of the crystallization process (i.e., within approximate to 40 ms), achieved by using continuous-flow microfluidic devices, can be used to enable novel crystallization pathways of a prototypical spin-crossover MOF towards its thermodynamic product. In particular, two distinct and unprecedented nucleation-growth pathways were experimentally observed when crystallization was triggered under microfluidic mixing. Full-atom molecular dynamics simulations also confirm the occurrence of these two distinct pathways during crystal growth. In sharp contrast, a crystallization by particle attachment was observed under bulk (turbulent) mixing. These unprecedented results provide a sound basis for understanding the growth of CPs and open up new avenues for the engineering of porous materials by using out-of-equilibrium conditions.
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