Unraveling the Intertwining Factors Underlying the Assembly of High-Nuclearity Heterometallic Clusters.

Two closely related yet distinctly different cationic clusters, [Dy 52 Ni 44 (HEIDA) 36 (OH) 138 (OAc) 24 (H 2 O) 30 ] 10+ (1) and [Dy 112 Ni 76 (HEIDA) 44 (EIDA) 24 (IDA) 4 (OH) 268 (OAc) 48 (H 2 O) 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 Dy 3+ and Ni 2+ , 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 for the kinetic product 2. By tuning these intertwining conditions, the reaction can be regulated toward a particular product.