The combination of the copper(I)–iodide entity with organic ligands gives rise to a large variety of Cu^II polynuclear structures in the form of molecular complexes or extended structures. An appropriate selection of these components allows the preparation of materials showing interesting physicochemical properties and potential applications, mainly focused on organic light-emitting diodes and optical sensors. The most prominent physical feature of these materials is their emission, which can be modulated using the chemical structure and composition. This review article collates the advances in this research field, rationalizing the information into two main blocks as a function of the dimensionality of the structures: molecular complexes and extended networks. We describe the most typical ways of preparation, structures, and properties, with particular attention to the processability of the material as a fundamental aspect of the integration of the materials into real devices. Therefore, we aim to integrate the basic elements of the coordination chemistry of Cu^II clusters from the materials science perspective to envision this promising research field's potential technological future.

Metal–organic cages are processable porous molecules that can be assembled into a range of macroscopic porous materials.

The simple direct synthesis of Cu(ii) and Ag(i) salts and thiobenzoic acid under ambient conditions allows the preparation of two bidimensional coordination polymers [M(TB)]_n (TB = thiobenzoate; M = Cu (1) or Ag (2)).

Flexible Metal–Organic Framework (MOF) composites can be designed to develop shapeshifting materials in which the propagation of the dynamic behavior of flexible MOFs from the nano- or mesoscale to the macroscale results into useful mechanical work.