Liquid reagents are not enough for liquid assisted grinding in the synthesis of [(AgBr)(n-pica)]n.

This study investigates the mechanochemical reactions between AgBr 3-picolylamine and 4-picolylamine. The use of different stoichiometry ratios of the reagents allows [(AgBr)(n-pica)]n and [(AgBr)2(n-pica)]n to be obtained, and we report the new structures of [(AgBr)2(3-pica)]n and [(AgBr)2(4-pica)]n which are characterized by the presence of the following: (a) infinite inorganic chains, (b) silver atom coordinated only by bromide atoms and (c) argentophilic interactions. Furthermore, we studied the interconversion of [(AgBr)(n-pica)]n/[(AgBr)2(n-pica)]n by mechanochemical and thermal properties. The in situ experiments suggest that [(AgBr)(3-pica)]n is kinetically favoured while [(AgBr)2(3-pica)]n is converted into [(AgBr)(3-pica)]n only with a high excess of the ligand. Finally, the liquid nature of the ligands is not sufficient to assist the grinding process, and the complete reaction is observed with the addition of a small quantity of acetonitrile.

AgX-based hybrid coordination polymers: mechanochemical synthesis, structure and luminescence property characterization.

Hybrid coordination polymers are interesting for their ability to converge the properties of both inorganic and organic systems in one single compound and recently attention has been focused on silver based hybrid coordination polymers due to their luminescence properties. We searched the CSD to establish the propensity of AgXL (X = Cl-, Br- and I-) with L as an organic ligand to form hybrid coordination polymers. About 800 AgXL structures are deposited in the CSD, with huge structural variability: indeed, it is possible to recognize some structural preferences based on the halide nature. The formation of an inorganic polymeric unit is favoured by iodide but it is also possible with the other halides. This research continues with the synthesis of AgX (X = I-, Br-) based coordination polymers with 2-, 3- and 4-picolylamine (n-pica) as ligands. By mechanochemical synthesis five new hybrid coordination polymers and one coordination polymer have been obtained and their structures determined. While [(AgI)(n-pica)]n are not luminescent, [(AgBr)(n-pica)]n emit and their profile depends on the crystallinity of the sample.