Metal-directed assembly of polyferrocenyl transition metal dithiocarbamate macrocyclic molecular boxes

Novel redox-active polyferrocenyl transition metal dithiocarbamate macrocyclic molecular boxes (10a–c), (11) and (12a–c) are synthesised by reaction of the respective ferrocenyl secondary amines, namely, N,N′-bis(ferrocenemethyl)-1,3-bis(aminomethyl)benzene (4), 1,1′-bis(benzylaminomethyl)ferrocene (8) and 1,1′-bis((ferrocenylmethyl)aminomethyl)ferrocene (9) with carbon disulfide, potassium hydroxide and transition metal (zinc, copper, nickel) acetate in high yields (52–82%) and characterised by spectroscopic and electrochemical techniques. The single-crystal X-ray structure of 10a shows that each zinc atom is in tetrahedral geometry, being bonded to two dithiocarbamate ligands with ZnS distances 2.32(1)–2.44(1) Å.