Metal-controlled self-assembly of arsenic–vanadium-cluster backbones with organic ligands

Abstract

Five new organic–inorganic assemblies, [Co(en)₃][Co(en)₂As₈V₁₄O₄₂(H₂O)]·16H₂O (1), [Ni(Meen)₃]₄[Ni(Meen)₂][As₈V₁₄O₄₂(NO₃)]₂·8H₂O (2), [Cd(en)₃][Cd(phen)(en)(H₂O)₂][(en)CdAs₈V₁₃O₄₁(H₂O)]·1.5H₂O (3), [Cd(phen)₂(en)]₂[(phen)CdAs₈V₁₃O₄₁(H₂O)]·21H₂O·phen (4), [Zn(en)₂]₂[(bpe)₂Zn₂As₈V₁₂O₄₀(H₂O)] (5) (en = ethylenediamine, Meen = 1,2-diaminopropane, phen = 1,10-phenanthroline, and bpe= 1,2-bis(4-pyridyl)ethylene) have been synthesized and characterized. Among them, compounds 1 and 2 are constructed from the [As₈V₁₄O₄₂] cluster; compounds 3 and 4 are constructed from the Cd-substituted polyoxovanadate [CdAs₈V₁₃O₄₁] cluster, while compound 5 consists of bizinic-substituted polyoxovanadate [Zn₂As₈V₁₂O₄₀] building units. It can be assumed that the metal ions used in these reaction systems play a crucial role in controlling the formation of the arsenic–vanadium–cluster backbones, and further leading to the formation of hybrids based on these clusters.