Defect‐Guided Assembly of Aperiodic and Flexible Metal–Organic Frameworks From Pre‐Formed Cages
Abstract
ABSTRACT Controlling the spatial distribution of defects in metal–organic frameworks (MOFs) remains a fundamental challenge in defect engineering. Here, we report a cage‐directed assembly strategy that enables the programmed introduction of topologically correlated defects and induces aperiodicity in HKUST‐1‐type frameworks. Pre‐synthesised Rh(II) metal–organic cages or polyhedra (MOPs) act as persistent cavities that template the formation of HKUST‐1‐based networks containing linker‐induced Cu‐vacancy domains confined within discrete cuboctahedral cavities. The use of dicarboxylate linkers, in which one carboxylate group is missing compared to the original 1,3,5‐benzenetricarboxylate linker, gives rise to nine distinct local defect configurations that are independently distributed throughout the lattice. This results in an aperiodic framework with preserved long‐range crystallinity. The resulting materials exhibit hierarchical micro–mesoporosity, reversible loss and recovery of crystallinity, and a pronounced solvent‐induced breathing response. This work demonstrates that combining pre‐formed cages with linkers with reduced connectivity can be a new strategy to localise defects and access aperiodic MOFs with emergent structural adaptability.
Article Details
Authors (13)
Francisco Sánchez‐Férez
Catalan Institute of Nanoscience and Nanotechnology (ICN2) CSIC and The Barcelona Institute of Science and Technology Campus UAB Barcelona Spain
Akim Khobotov‐Bakishev
Catalan Institute of Nanoscience and Nanotechnology (ICN2) CSIC and The Barcelona Institute of Science and Technology Campus UAB Barcelona Spain
Borja Ortín‐Rubio
Catalan Institute of Nanoscience and Nanotechnology (ICN2) CSIC and The Barcelona Institute of Science and Technology Campus UAB Barcelona Spain
Cornelia von Baeckman
Catalan Institute of Nanoscience and Nanotechnology (ICN2) CSIC and The Barcelona Institute of Science and Technology Campus UAB Barcelona Spain
Laura Hernández‐López
Catalan Institute of Nanoscience and Nanotechnology (ICN2) CSIC and The Barcelona Institute of Science and Technology Campus UAB Barcelona Spain
Alba Cortés‐Martínez
Catalan Institute of Nanoscience and Nanotechnology (ICN2) CSIC and The Barcelona Institute of Science and Technology Campus UAB Barcelona Spain
Robert A. I. Paraoan
Inorganic Chemistry Laboratory Department of Chemistry University of Oxford Oxford UK
Roberto Boada
Department of Chemistry Faculty of Science Universitat Autònoma de Barcelona (UAB) Barcelona Spain
Judith Juanhuix
ALBA Synchrotron Light Facility Barcelona Spain
Felipe Gándara
Materials Science Institute of Madrid, CSIC, Sor Juana Inés de la Cruz 3, Madrid 28049, Spain
Andrew L. Goodwin
Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K.
Arnau Carné‐Sánchez
Catalan Institute of Nanoscience and Nanotechnology (ICN2) CSIC and The Barcelona Institute of Science and Technology Campus UAB Barcelona Spain
Daniel Maspoch
Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC, and The Barcelona Institute of Science and Technology