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The role of anion in supramolecular aggregation and energetic properties in a series of Cd picolinamide complexes

A novel group of energetic compounds, known as energetic coordination polymers (ECPs), can be rationally designed by introducing of highly energetic ions like ClO4-, N3–, NO3– and NO2– into a polymeric framework. Herein we report the preparation of four novel cadmium(II) complexes with picolinamide (pia) as ligand and different ions: [Cd(pia)3](ClO4)2·2H2O (1), [Cd(NO3)(ac)(pia)2] (2), [Cd(NO2)2(pia)2] (3), [Cd2(μ1, 1-N3)4(pia)2]n [Cd(μ1, 1-N3)2(pia)]n (4). The presence of different anions from starting Cd(II) salts caused the formation of discrete coordination compounds(1, 2 and 3), and coordination polymer (4). In 2, 3 and 4 anions are coordinated to Cd(II), while in 1 perchlorate anions act as a counterion. The molecular and crystal structure analysis has shown that in all compounds pia acts as N, O-chelator in various coordination arrangements depending on the present anion (1, 2 and 4 - distorted octahedral, 3- distorted square antiprismatic). In the crystal structures, the dominant mode of intermolecular interaction is a strong head−to−head amide hydrogen bond, with exception of 1. Structural analysis of herein-reported compounds and previously described Cd(pia)A (A – anion) compounds has shown that bulky tetrahedral anions (ClO4- and SO42-) inhibit the formation of the strong head−to−head amide hydrogen bonds. The investigations of energetic properties and sensitivity indicate a possible application of compound 4 as a secondary explosive material with energetic properties like those of LA (lead azide), mercury fulminate, or ammonium nitrate.

Cadmium(II) complexes Picolinamide Anions Crystal structure Energetic materials Coordination polymer

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