This review focuses on the emergence of supramolecular functions arising from the synergy between thiacalixarene and other components, particularly metal ions. The functions described in this review are separation, catalysis, cage formation, magnetism, luminescence, and sensing, which are not realized by covalent modification of the thiacalixarenes. Fundamental functions such as inclusion and complexation, as well as some new synthetic and modification methods of thiacalixarene, will be discussed prior to discussing the supramolecular functions. The examples also cover the cases of other sulfur-bridged entities: sulfinyl- and sulfonylcalixarenes. Emphasis is placed on the fact that the multifunctionality of the sulfur-bridged calixarene is the key to realize these supramolecular functions. This is almost the sole reason why thiacalixarene is valuable in chemistry.
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