Supramolecular assemblies with water-soluble p-sulfonatothiacalix[6]arene lanthanide complexes: one-dimensional 'ladder-type' coordination polymers and one-dimensional hydrogen-bonded polymers

Crystals of La and Ce complexes of water-soluble p-sulfonatothiacalix[6]arenes showed that thiacalixarene molecules adopt a 1,2,3-alternate conformation. In contrast, crystals of Eu, Tb, Tm, Yb, and Lu complexes of p-sulfonatothiacalix[6] arenes indicated that thiacalixarene molecules maintain an 'up-down' double partial-cone conformation. In the extended structures of the La and Ce complexes, a one-dimensional 'ladder-type' coordination polymer was formed via direct coordination of the sulfonate groups of the thiacalixarene molecules to the aquated metal cations. Three-dimensional supramolecular network assemblies are constructed from the piles of 'ladder-type' polymers formed via hydrogen bonds, O center dot center dot center dot O and S center dot center dot center dot S interactions, and S-pi interactions. In contrast, the extended structures of the Eu, Tb, Tm, Yb, and Lu complexes form via mutually supporting intermolecular pi-pi stacking, S-pi interactions, and hydrogen-bonding interactions between two differently directed polymers.