Three metallacryptate supramolecular assemblies have been obtained using salicylhydroxamic acid derivatives (H3L). The three ligands differ in the residue at the para position with respect to the hydroxamic function (-H, -NH2, and -(4-pyridyl)). The core of these supramolecules correspond to the formula [(Mn-II)(2)(Mn-III)(9)(mu(3)-O)(4)(OAc)(3)(Shi)(6)](2+) (abbreviated as Mn11L6) in all three compounds. Additional acetate or hydroxide ions and DMF molecules are coordinated to the Mn-III ions. With L3- = Shi(3-) the Mn11L6 units assemble into a nonporous structure, where the metallacryptates are linked together through Na-I ions bridging between the units. Conversely, with L3- = p-aShi(3-) (NH2 group) and p-pyShi(3-) (4-pyridyl group) the units assemble in parallel chains and into a MOF-like structure, respectively. In both solids, a honeycomb porous architecture was obtained, where infinite channels run along the crystal structure. With p-aShi(3-), Na-I bridging ions and hydrogen bonds, provided by the presence of the amino group, characterize the interactions between the parallel chains of supramolecules. On the other hand, with p-pyShi(3-), the peripheral pyridyl groups point away from the metallacryptate units and are coordinated to available positions on Mn-III ions of neighboring molecules, with formation of a peculiar porous-coordination polymeric architecture.
Three-Dimensional Porous Architectures Based on Mn II/III Three-Blade Paddle Wheel Metallacryptates / Marzaroli, V.; Spigolon, G.; Lococciolo, G.; Quaretti, M.; Salviati, C.; Kampf, J. W.; Licini, G.; Marchio, L.; Pecoraro, V. L.; Tegoni, M.. - In: CRYSTAL GROWTH & DESIGN. - ISSN 1528-7483. - 19:3(2019), pp. 1954-1964. [10.1021/acs.cgd.8b01921]
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