Unraveling the Intertwining Factors Underlying the Assembly of High‐Nuclearity Heterometallic Clusters

Abstract

Two closely related yet distinctly different cationic clusters, [Dy52Ni44(HEIDA)36(OH)138(OAc)24(H2O)30]10+ (1) and [Dy112Ni76(HEIDA)44(EIDA)24(IDA)4(OH)268(OAc)48(H2O)44]4+ (2) (HEIDA = N‐(2‐hydroxyethyl)iminodiacetate), each featuring a multi‐shell core of Platonic and Archimedean polyhedra, were obtained. Depending on the specific conditions used for the co‐hydrolysis of Dy3+ and Ni2+, the product can be crystallized out as one particular type of cluster or as a mixture of 1 and 2. How the reaction process was affected by the amount of hydrolysis‐facilitating base and/or by the reaction temperature and duration was investigated. It has been found that a reaction at a high temperature and/or for an extended period favors the formation of the compact and thermodynamically more stable 1, while a brief reaction with a large amount of the base is good to the kinetic product 2. By tuning these intertwining conditions, the reaction can be regulated toward a particular product.