ABSTRACT: The hexatopic ligands 1,3,5-tris(4,2':6',4''-terpyridin-4'-yl)benzene (1), 1,3,5-tris(3,2':6',3''-terpyridin-4'-yl)benzene (2), 1,3,5-tris{4-(4,2':6',4''-terpyridin-4'-yl)phenyl}benzene (3), 1,3,5-tris{4-(3,2':6',3''-terpyridin-4'-yl)phenyl}benzene (4) and 1,3,5-trimethyl-2,4,6-tris{4-(3,2':6',3''-terpyridin-4'-yl)phenyl}benzene (5) have been prepared and characterized. The single crystal structure of 1·1.75DMF was determined; 1 exhibits a propeller-shaped geometry with each of the three 4,2':6',4''-tpy domains being crystallographically independent. Packing of molecules of 1 is dominated by face-to-face π-stacking interactions which is consistent with the low solubility of 1 in common organic solvents. Reaction of 5 with [Cu(hfacac)2]·H2O (Hhfacac = 1,1,1,5,5,5-hexaf
