MOLECULAR-COMPLEXES OF MACROCYCLIC POLYAMINES WITH PI-ELECTRON ACCEPTORS

The charge-transfer interaction of macrocyclic polyamines 1,4,8,11-tet raazacyclotetradecane (TACTD); 1,4,8,12-tetraazacyclopentadecane (TACP D) and 8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (TMTACTD) wi th chloranil (CHL), tetracyanoethylene (TCNE) and 2,3-dichloro-5,6-dic yano-1,4-benzoquinone (DDQ) as pi-electron acceptors was investigated spectroscopically. Spectral characteristics and stability constants of formed CT complexes are examined and discussed in terms of molecular structure of both electron donor and acceptor as well as solvent polar ity. It is deduced that the CT complexes are of strong kind where macr ocyclic polyamines-DDQ, TMTACTD-TCNE, -CHL complexes essentially exist in the dissociated state (radical cations and anions D+, A-). On the other hand, the TCNE and CHL complexes with TACTD and TACPD exist in a dative structure (D+-A-). Solid 1:1 CT complexes are synthesized and characterized.