The preparation and rational design of nanosized clusters (M) 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); (3) metallamacrocycles (up to M); (4) pocket-like (M or M) or square-like species (M) 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). 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.

中文翻译：

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Thiacalix[4]芳烃大环化合物作为多功能构建模块，用于合理设计高核金属簇、金属大环化合物、多孔配位笼和容器

在存在/不存在来自不同附加配体的O和N供体原子的情况下，分析了基于锥形构象大环硫杂[4]芳烃骨架的纳米簇(M)和笼的制备和合理设计。对此类大环配体的配位能力进行了回顾，从而产生了如下超分子物种：（1）金属（Ag，Au）核纳米粒子，装饰有有机硫杂[4]芳烃衍生物壳； (2) 不同类型的高核团簇（最多M）； (3) 金属大环（最多M）； (4) 袋状（M 或 M）或方形物种 (M) 呈现内部和外部孔隙率 (5) 八面体笼，涉及 8 或 12 个外部配体铺平八面体的面或边缘 (6) 更高核度的物种（最多 M）。对于袋状、方形和八面体物种，如系统分析所示，通过使用明智选择的有机配体，它们的形成已合理化。人们特别关注这些有限物质的结构/性质关系：磁性、发光、气体吸附、分子识别和催化性质。还讨论了这个新兴领域的前景和未来挑战。