X-ray Structure and Electrochemical Properties of Ferrocene-Substituted Metalloporphyrins

• Published in: Bulletin of the Korean Chemical Society Vol. 22; no. 12; pp. 1316 - 1322
• Main Authors: 김진원, 이석우, 나용환, 이기평, 도영규, 정세채, Kim, Jin Won, Lee, Seok U, Na, Yong Hwan, Lee, Gi Pyeong, Do, Yeong Gyu, Jeong, Se Chae
• Format: Journal Article
• Language: Korean
• Published: 2001
• Subjects: pi$-Conjugation; Porphyrins; Ferrocene; Electrochemical
• ISSN: 0253-2964; 1229-5949

Transition metal complexes of novel mono- and di-ferrocene-substituted porphyrins have been synthesized and characterized by structural and electrochemical methods. The X-ray structures of Mn(FPTTP)Cl and Mn(DFTTP)Cl showed the distorted square pyramidal coordination geometry with syn configuration of chloride and ferrocenyl substituents. The electrochemistry of ferrocene-substituted porphyrins and their metal complexes has been determined to elucidate the ${\pi}-conjugation$ effect of the porphyrin ring. The ferrocenyl group of H2FPTTP underwent a reversible one-electron transfer process at 0.30 V, indicating the good electron donating effect of the phorphyrin ring to the ferrocene substituent. The redox potential of the ferrocenyl subunit and porphyrin ring was affected by the central metal ions of the metalloporphyrins, that is, Zn(II) and Ni(II) made the oxidation of ferrocene much easier and Mn(III) made it harder. The ferrocene subunits of H2DFTTP interacted electrochemically with each other with peak splitting of 0.21 V. The strength of the electrochemical interactions between the two ferrocenyl substituents can be controlled by central metal ions of metalloporphyrins.