Sie befinden Sich nicht im Netzwerk der Universität Paderborn. Der Zugriff auf elektronische Ressourcen ist gegebenenfalls nur via VPN oder Shibboleth (DFN-AAI) möglich. mehr Informationen...
This work reports a series of covalently linked hybrids comprising 5,10,15,20‐tetraaryl‐5,15‐diazaporphyrinoids (M‐TADAP; M = Ni, Zn, Cu) and amines. M‐TADAP‐amine hybrids were prepared via the metal‐templated cyclization of the corresponding metal(II)‐dipyrrin complexes and redox reactions on the DAP unit. In the UV/vis/near‐IR absorption spectra of the hybrids containing an 18π‐electron DAP ring, broad charge‐transfer bands were observed, reflecting the electron‐donating property of the para‐aminophenyl groups and the electron‐accepting property of the 18π TADAP dication. The electrochemical behavior of the M‐TADAP‐amine hybrids was strongly dependent on the structure of the peripheral amine units. Further electrochemical oxidation of the hybrids bearing N‐Ph groups conceivably generated amine‐centered radicals, which sequentially underwent irreversible coupling to form benzidine‐linked M‐TADAP polymer films. The Ni‐TADAP‐benzidine polymer exhibited the electric conductivity of 2×10−3 S m−1.
A series of covalently linked hybrids of metal complexes of 5,10,15,20‐tetraaryl‐5,15‐diazaporphyrinoids (M‐TADAP) and tertiary/secondary amines were prepared. The amine units exerted a significant impact on the electrochemical behavior of the M‐TADAP‐amine hybrids, of which the para‐NPh2 derivatives were electrochemically polymerized to afford the corresponding M‐TADAP‐benzidine polymers.