The syntheses and properties of expanded 4- tert -butyl-mercapto-calixarenes, in which the methylene linkers are replaced by -CH 2 NRCH 2 - or -CH 2 NRCH 2 - and CH 2 NRCH 2 CH 2 CH 2 NRCH 2 - units, are described. The new macrocycles were obtained in a step-wise manner, utilizing fully protected, i.e. S-alkylated, derivatives of the oxidation-sensitive thiophenols in the cyclisation steps. Reductive cleavage of the macrobicyclic or macrotricyclic intermediates ( 6 , 7 , 11 ) afforded the free thiophenols (H 4 8 , H 4 9 , and H 4 12 ) in preparative yields as their hydrochloride salts. The protected proligands can exist in two conformations, resembling the "cone" and "1,3-alternate" conformations found for the parent calixarenes. The free macro-cycles do not show conformational isomerism, but are readily oxidized forming intramolecular disulfide linkages. Preliminary complexation experiments show that these expanded mercaptocalixarenes can serve as supporting ligands for tetranuclear thiolato clusters.