An aza-terpyridinophane receptor containing the polyamine 4,7,10,13-tetraazahexadecane-1,16-diamine linked through methylene groups to the 5,5″ positions of a terpyridine unit has been prepared and characterized (L). The acid-base behaviour, CuII speciation and ability to form ternary complexes (CuII-L-carbonate) have been explored by potentiometric titrations in 0.15 M NaClO4 and by UV/Vis and paramagnetic NMR spectroscopy. Comparisons are made with a previously reported terpyridinophane containing the polyamine 4,7,10-triazatridecane-1,13-diamine (L1). For this latter receptor, reductive coupling between indigo and carbon dioxide at indigo-modified electrodes produces carboxylated derivatives via a solid-state reaction under electrochemical activation.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)