Construction and catalytic effects of solvent- and metal(ii)-dependent products: the process of transformation of 0D structures into 3D structures

Abstract

Self-assembly of Zn(NO₃)₂ with tris(2-(isoquinolin-5-yloxy)ethyl)amine (L) as a C₃-symmetric tridentate N-donor in a mixture of dioxane and acetonitrile gives rise to [NO₃@Zn₃(NO₃)₅L₂]·2CH₃CN in the form of crystals of sandwich-shaped cages encapsulating a nitrate, whereas the same self-assembly reaction in a different mixture, benzene and ethanol, produces [Zn(NO₃)L(H₂O)]NO₃·H₂O in the form of crystals of 3D networks with cml {4,6²}₂{4²,6¹⁰,8³} topology. The most interesting feature is the transformation of [NO₃@Zn₃(NO₃)₅L₂]·2CH₃CN crystals into [Zn(NO₃)L(H₂O)]NO₃·H₂O crystals in ethanol. A significant difference in heterogeneous transesterification catalysis between the two species is observed. On the other hand, self-assembly of Co(NO₃)₂ with L gives rise to 3D networks, [Co(NO₃)L(H₂O)]NO₃·H₂O, whereas self-assembly of Ni(NO₃)₂ and Cu(NO₃)₂ with L produces sandwich-type cages, [NO₃@Ni₃(NO₃)₃L₂(H₂O)₆]2NO₃·C₂H₅OH·C₆H₆ and [NO₃@Cu₃(NO₃)₅L₂(C₂H₅OH)]·C₂H₅OH·2C₆H₆, respectively, with the latter notably showing heterogeneous catechol oxidation catalytic effects.