Ligand-Oxidation-Based Anodic Synthesis of Oriented Films of Conductive M-Catecholate Metal–Organic Frameworks with Controllable Thickness

Effective control over the crystallization of metal-organic framework (MOF) films is of great importance not only for the performance study and optimization in related applications but also for the fundamental understanding of the involved reticular chemistry. Featuring many technological advantages, electrochemical synthesis has been extensively reported for many MOF materials but is still challenged by the production of dense oriented films with a large-range tuning of thickness. Here, we report a ligand-oxidation-based anodic strategy capable of synthesizing oriented films of two-dimensional (2D) and three-dimensional (3D) conductive M-catecholate MOFs (2D Cu₃(HHTP)₂, 2D Zn₃(HHTP)₂, 2D Co₃(HHTP)₂, 3D YbHHTP, and 2D Cu₂TBA) with tunable thicknesses up to tens of micrometers on commonly used electrodes. This anodic strategy relies on the oxidation of redox-active catechol ligands and follows a stepwise electrochemical-chemical reaction mechanism to achieve effective control over crystallizing M-catecholate MOFs into films oriented in the [001] direction. Benefiting from the electrically conductive nature, Cu₃(HHTP)₂ films could be thickened at a steady rate (17.4 nm·min^-1) from ∼90 nm to 10.7 μm via a growth mechanism differing from those adopted in previous electrochemical synthesis of dense MOF films with limited thickness due to the self-inhibition effect. This anodic synthesis could be further combined with a templating strategy to fabricate not only films with well-defined 2D features in sizes from micrometers to millimeters but also high aspect ratio mesostructures, such as nanorods, of Cu₃(HHTP)₂.