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Exploiting Reaction‐Diffusion Conditions to Trigger Pathway Complexity in the Growth of a MOF
Author(s) -
Calvo Galve Néstor,
Abrishamkar Afshin,
Sorrenti Alessandro,
Di Rienzo Lorenzo,
Satta Mauro,
D'Abramo Marco,
Coronado Eugenio,
Mello Andrew J.,
Mínguez Espallargas Guillermo,
PuigmartíLuis Josep
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202101611
Subject(s) - crystallization , nucleation , crystal growth , microfluidics , mixing (physics) , materials science , nanotechnology , chemical physics , diffusion , chemical engineering , chemistry , crystallography , thermodynamics , physics , organic chemistry , quantum mechanics , engineering
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 ≈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.