Modular approach towards functional multimetallic coordination clusters

Polynuclear coordination clusters (PCCs) provide considerable design capabilities towards various functions based on structural non-rigidity and spin state transitions, optical performance, catalytic properties and porosity. The elaboration of new synthetic pathways is fundamental towards advanced switchable and sensing materials, however, the recognition of the structure-property correlations and their optimization is also a key issue. In this context, the current review underlines the role of internal and external functionalization of recognized discrete cluster cores, as the basis for well-designed performance. In particular, we present here the essential update on the recent advances in the overall functionalization of polycyanido-bridged cores (chapter 2). Moreover, we discuss the polymetallic coordination cores constructed with other ligands (short oxido-, hydroxido-, chalcogenido- and other bridges as well as by long multitopic panelling ligands) by indicating the examples of solid-solutions and site selective occupation along the mixed-metal cluster cores (chapter 3), and external decoration of such clusters with ligands, complexes and polynuclear fragments (chapter 4). We also highlight the key properties, indicate the structure-property correlations, and show the power and limitations of the methods used in the presented studies. Finally, we provide the comparison between cyanido-bridged systems and other systems, and indicating possible future research pathways towards the development of PCCs based multicomponent functional systems. (C) 2020 Elsevier B.V. All rights reserved.