Thiacalix[4]arene macrocycles as versatile building blocks for the rational design of high-nuclearity metallic clusters, metallamacrocycles, porous coordination cages and containers.

• Coordination finite species based on thiacalix[4]arene macrocyclic backbones are reviewed. • The coordination abilities of calixarene based ligands towards metals are presented. • The effect of additional ligands on the nuclearity and shape of the finite species is discussed. • The useful properties of the resulting intriguing architectures are highlighted. The preparation and rational design of nanosized clusters (M n) and cages based on the macrocyclic thiacalix[4]arene backbone in cone conformation has been analysed in the presence/absence of O and N donor atoms from different additional ligands. The coordination abilities of this class of macrocyclic ligands is reviewed leading to supramolecular species like: (1) metallic (Ag, Au) core Nanoparticles decorated with an organic thiacalix[4]arene derivatives shell; (2) different types of high nuclearity clusters (up to M 32); (3) metallamacrocycles (up to M 30); (4) pocket-like (M 6 or M 8) or square-like species (M 16) presenting internal and external porosity (5) octahedral cages involving 8 or 12 external ligands paving the faces or edges of the octahedron (6) species of higher nuclearity (up to M 72). For the pocket-like, square-like and octahedral species, their formation has been rationalized by the use of judiciously chosen organic ligands, as shown by the systematic analysis. A special attention has been drawn to the structure/properties relationships of these finite species: magnetic, luminescence, gas sorption, molecular recognition and catalytic properties. Perspectives and future challenges in this emerging field are also discussed. [ABSTRACT FROM AUTHOR]