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

Abstract 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‐ h ydroxyethyl)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.