Molecularly designed architectures--the metalloligand way.

Designed materials offer noteworthy applications which are often architecture dependent. Despite knowing such a fact, one of the major challenges faced by the scientific community is to find ways to predict and, if possible, control the resultant architecture of a network. If such an exercise is fruitful, it creates enormous opportunities to synthesize exotic materials with tailor-made applications. Any network is composed of individual molecules and the transition from a single molecule to a network can be achieved through several routes taking advantage of synthetic chemistry. There exists a molecular building block at the heart of such a transition which mediates such a process from a single molecule to a network. Although a large number of building blocks have created assorted materials, utilization of a well-defined coordination complex as the building block (i.e., metalloligand) is unique for the construction of a designed architecture. A coordination complex as the building block offers structural rigidity that places the auxiliary functional groups to a pre-organized conformation. Such auxiliary functional groups could then coordinate a secondary metal ion or be involved in the self-assembly via weak interactions, such as hydrogen bonds. This review focuses on the recent progress achieved through assorted molecular building blocks towards generating ordered networks. Broadly, two classes of metalloligands will be discussed: those offering hydrogen bond sensitive functional groups and those tendering coordination bond responsive groups. Nevertheless, the result is the construction of networks of a highly-ordered nature in both cases. The present review is expected to provide new strategies for constructing functional materials through metalloligands for challenging and practical applications.