Hierarchical Assembly of Coordination Macromolecules with Atypical Geometries: Gd44Co28 Crown and Gd95Co60 Cage.

The discovered giant clusters are always highly symmetric owing to the spontaneous assembly of one or two basic units. Herein we report the Gd44Co28 crown and Gd95Co60 cage, formulated as [Gd44Co28(IDA)20 (OH)72(CO3)12(OAc)28(H2O)64]⋅(ClO4)24 and [Na4Gd95 Co60(IDA)40(OH)150(CO3)40(OAc)58(H2O)164] ⋅ (ClO4)41 (H2IDA=iminodiacetic acid), respectively, by providing a library containing multiple low‐nuclearity units. The heart‐like units and crown‐like tetramer found in both compounds indicate unprecedented assembly levels, leading to an atypical geometry characteristic compared to the giant clusters directly assembled by regular units. These two clusters not only significantly increase the size of Ln−Co clusters but also exhibit the enhanced magnetic entropy change at ultra‐low temperatures. This work provided an effective way to fabricate cluster compounds with giant size and geometry complexity simultaneously. [ABSTRACT FROM AUTHOR]