Year: 2026
Type: preprint
Abstract: The ability to program the shape of single crystals through molten-state processing has transformed the manufacturing of inorganic materials, yet this strategy is fundamentally incompatible with most organic-based crystals, which decompose before melting. Here, we show that a non-classical crystallization pathway can overcome this limitation by generating a moldable dense-liquid intermediate during the growth of peptide-based metal-organic frameworks (MOFs). By engineering a reaction environment in which precursor concentration and reagent diffusion are controlled while suppressing convection, we selectively activate a liquid-liquid phase separation process to produce a confined dense-liquid phase that can be shaped prior to crystallization. Repeated diffusion-limited chemical perturbations subsequently transform this intermediate into single crystals that faithfully preserve the geometry of the confined environment in which they form, enabling non-equilibrium morphologies inaccessible by conventional synthesis. We further show that crystal shape influences mechanical properties, demonstrating that controlling crystallization pathways provides a route to tailor function without altering chemical composition.
Source: ChemRxiv
Institutions: Universitat de Barcelona, Universidade do Porto, Centro de Estudos de Fenómenos de Transporte, Institut de Nanociència i Nanotecnologia de la Universitat de Barcelona, Institute for Bioengineering of Catalonia, ETH Zurich, Institute of Robotics and Intelligent Systems, Institució Catalana de Recerca i Estudis Avançats
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7220705051