Coexistence of Water Dimer and Hexamer Clusters in 3D Metal-Organic Framework Structures of Ce(III) and Pr(III) with Pyridine-2,6-dicarboxylic Acid

High-energy nitrogen-rich pentazolides of groups 6 and 13-16 are studied theoretically. Many of them have experimentally known azide analogues. Our highest nitrogen-to-element ratio of 40:1 is achieved in the systems [M(N5)8]2- (M = Cr, Mo, W). The thermodynamic and kinetic stability of the studied systems grows with the negative charge on the system and is highest for tetra-pentazolides and hexa-pentazolides of B, Al, and Si. Systems such as B(N5)4 - or Si(N5)6 2- are examples of the most stable candidates for these new species. N(N5)2- is a candidate for a new all-nitrogen system. Neutral and positive systems were less stable. Pentazole derivatives of "dinuclear" C2Hn and N2Hn systems were investigated and were found to be of comparable stability as their "mononuclear" analogues. Pentazole derivatives of benzene, the C6H6-n(N5)n (n = 2, 3, 6) systems, have a similar stability as the experimentally known phenylpentazole. A borazine analogue, N3B3H3(N5)3 is predicted to be one of the most stable systems of this family.