Mechanochemical Reactivity of Square‐Planar Nickel Complexes and Pyridyl‐Based Spacers for the Solid‐State Preparation of Coordination Polymers: The Case of Nickel Diethyldithiophosphate and 4,4′‐Bipyridine

The mechanochemical synthesis of a coordination polymer from a preformed metal coordination complex and a pyridyl‐based spacer has been successfully performed. The coordination polymer (1·L)∞ was obtained rapidly from the reaction of the neutral square‐planar complex [{(EtO)2PS2}2Ni] (1) and 4,4′‐bipyridine (L) at room temperature through two different mechanochemical approaches (neat grinding and liquid‐assisted grinding). The products were characterized by X‐ray powder diffraction, IR spectroscopy, scanning electron microscopy, thermogravimetry and differential scanning calorimetry techniques. In parallel (1·L)∞ was prepared by conventional solvent‐based methods, and the X‐ray crystal structure of the polymer, obtained as single crystals, was compared with that from the mechanochemical preparation. An environmentally friendly one‐pot mechanosynthesis of an NiII coordination polymer starting from a square‐planar nickel complex and a pyridyl‐based spacer, namely, the coordinatively unsaturated (dithiophosphato)NiII complex [{(EtO)2PS2}2Ni] and 4,4′‐bipyiridine, is developed.