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

• Published in: Coordination chemistry reviews Vol. 513; p. 215846
• Main Authors: Khariushin, Ivan V., Bulach, Véronique, Solovieva, Svetlana E., Antipin, Igor S., Ovsyannikov, Alexander S., Ferlay, Sylvie
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-08-2024; Elsevier
• Subjects: Chemical Sciences; Clusters; Coordination Cages; Metal Organic Polyhedra; Metallamacrocycles; Properties; TetraMercaptoThiaCalixArene; TetraSulfonylThiaCalixArene; ThiaCalixArene; ThiaCalixArene; TetraMercaptoThiaCalixArene; TetraSulfonylThiaCalixArene; Clusters; Metallamacrocycles; Coordination Cages; Metal Organic Polyhedra; Properties; ThiaCalixArene TetraSulfonylThiaCalixArene TetraMercaptoThiaCalixArene Clusters Coordination Cages Metal Organic Polyhedra Metallamacrocycles Properties
• ISSN: 0010-8545; 1873-3840; 0010-8545
• DOI: 10.1016/j.ccr.2024.215846

•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 (Mn) 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 M32); (3) metallamacrocycles (up to M30); (4) pocket-like (M6 or M8) or square-like species (M16) 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 M72). 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.