Palladium(II)‐Based Self‐Assembled Heteroleptic Coordination Architectures: A Growing Family

Abstract Metal‐driven self‐assembly is one of the most effective approaches to lucidly design a large range of discrete 2D and 3D coordination architectures/complexes. Palladium(II)‐based self‐assembled coordination architectures are usually prepared by using suitable metal components, in either a partially protected form (PdL′) or typical form (Pd; charges are not shown), and designed ligand components. The self‐assembled molecules prepared by using a metal component and only one type of bi‐ or polydentate ligand (L) can be classified in the homoleptic series of complexes. On the other hand, the less explored heteroleptic series of complexes are obtained by using a metal component and at least two different types of non‐chelating bi‐ or polydentate ligands (such as L a and L b ). Methods that allow the controlled generation of single, discrete heteroleptic complexes are less understood. A survey of palladium(II)‐based self‐assembled coordination cages that are heteroleptic has been made. This review article illustrates a systematic collection of such architectures and credible justification of their formation, along with reported functional aspects of the complexes. The collected heteroleptic assemblies are classified here into three sections: 1) (PdL′) m (L a ) x (L b ) y ‐type complexes, in which the denticity of L a and L b is equal; 2) (PdL′) m (L a ) x (L b ) y ‐type complexes, in which the denticity of L a and L b is different; and 3) Pd m (L a ) x (L b ) y ‐type complexes, in which the denticity of L a and L b is equal. Representative examples of some important homoleptic architectures are also provided, wherever possible, to set a background for a better understanding of the related heteroleptic versions. The purpose of this review is to pave the way for the construction of several unique heteroleptic coordination assemblies that might exhibit emergent supramolecular functions.