Exploring metal carbamates as precursors for the synthesis of metal–organic frameworks

Abstract

In the synthesis of metal–organic frameworks (MOFs), the choice of the metal precursor plays a key role because of the influence that it can exert on the crystallization kinetics. The present work explores the use of metal-carbamato complexes for the synthesis of benchmark MOFs, namely HKUST-1 and UiO-66. Cu₂(O₂CNEt₂)₄·2NHEt₂ and Zr(O₂CNEt₂)₄, prepared using straightforward CO₂ fixation reactions starting from the corresponding metal chlorides and diethylamine, were employed as metal precursors for MOF formation. The synthesis conditions, including the solvent, temperature, and ligand protonation degree, were systematically investigated, revealing metal carbamates as highly reactive precursors due to their prompt release of CO₂ and amine upon reaction with protic species, i.e., the polycarboxylic linkers. This property of metal carbamates allowed us to identify room temperature protocols to achieve MOFs with comparable properties to those obtained using traditional metal precursors. Subsequent optimization of the reaction conditions led to the design of a one-pot synthetic strategy for HKUST-1, starting directly from copper(II) chloride and diethylamine under a CO₂ atmosphere. The MOFs were characterized using various techniques, including powder X-ray diffraction, N₂ sorption analysis, ¹H nuclear magnetic resonance spectroscopy, and CHN elemental analysis, and compared to reference samples prepared according to literature procedures.