Three new organic tectons (2–4) based on the p-tert-butylthiacalix[4]arene backbone, blocked in the 1,3-alternate conformation, bearing four pyridyl coordinating moieties, have been synthesised and characterised in the solid state. The ligands are positional isomers and differ by the position of the N atom on the pyridyl unit (ortho for 2, meta for 3 and para for 4). Their combination with the Ag+ cation leads, reproducibly, to the formation of 2- and 3-D infinite silver coordination networks. Independent of the nature of the anion, the combination of 2 offering four (N,S) type chelates with the Ag+ cation affords an unprecedented diamond type 3D network. Both 3 and 4, behaving as tetrakis monodentate ligands, lead to the formation of 2-D architectures.

A series of thiacalix[4]arene derivatives blocked in the 1,3-alternate conformation and bearing four carboxylic acids have been designed and synthesized. These compounds, owing to the H-bond donor (OH moiety) and acceptor (CO group) nature of the carboxylic acid moieties, behave as self-complementary tectons and lead to the formation of tubular 1D H-bonded networks in the crystalline phase. Upon deprotonation of the self-complementary neutral compounds, i.e. transformation of carboxylic acid moieties into carboxylates, anionic tectons are generated. Due to their propensity to form H-bonded networks in the presence of a dicationic H-bond donor tecton of the cyclic bis-amidinium type, designed to behave as a molecular staple interconnecting two carboxylates moieties, 1-and 2-D H-bonded networks are formed under self-assembly conditions.