Metal-directed assembly of polyferrocenyl transition metal dithiocarbamatemacrocyclic molecular boxes

Novel redox-active polyferrocenyl transition metal dithiocarbamate macrocyc lic molecular boxes (10a-c), (11) and (12a-c) are synthesised by reaction o f the respective ferrocenyl secondary amines, namely, N,N'-bis(ferrocenemet hyl)-1,3-bis(aminomethyl)benzene (4), 1,1'-bis(benzylaminomethyl)ferrocene (8) and 1,1'-bis((ferrocenylmethyl)aminomethyl)ferrocene (9) with carbon di sulfide, potassium hydroxide and transition metal (zinc, copper, nickel) ac etate in high yields (52-82%) and characterised by spectroscopic and electr ochemical techniques. The single-crystal X-ray structure of 10a shows that each zinc atom is in tetrahedral geometry, being bonded to two dithiocarbam ate ligands with Zn-S distances 2.32(1)-2.44(1) . (C) 2001 Elsevier Science B.V. All rights reserved.