Thiacalix[4]-bis-crown-5 (L) was employed as a model host molecule, which shows both HSAB concept and endo/exo-coordination modes. In the K + complexations, a dinuclear complex [K 2 (L)](ClO 4 ) 2 ·CH 3 CN (1) as well as a mononuclear complex [K(L)][Pt(tht)Cl 5 ] (2) (tht = tetrahydrothiophene) were isolated: the latter as first example in such symmetrical hosts. Each K + in both species is stabilized not only by K + -O bondings (hard acid -hard base) in the crown cavities (endo-coordination) but also by K + -π interactions. The Ag + complexations afforded infinite products (3 and 4) in which the Ag + binds to the sulphur bridges (soft acid -soft base) from outside the cavity [a]

Thiacalix[4]arene-bis-1,2;3,4-crown-2 (basket or L) was isolated. Herein we report the first examples of the calix basket complexes. The combination of the basket and silver(I) salts afforded anion-dependent coordination polymers with different dimensionalities. The AgClO 4 complex 1, {[Ag 2 (L)(CH 3 OH)(ClO 4 ) 2 ]·4CHCl 3 } n has a 2-D square-grid network, [a]