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.