Coherent nuclear dynamics in ultrafast electron transfer in a porphyrin-ferrocene dyad

• Published in: Chemical physics letters Vol. 429; no. 1; pp. 91 - 96
• Main Authors: Kubo, Minoru, Mori, Yukie, Otani, Masana, Murakami, Masataka, Ishibashi, Yukihide, Yasuda, Masakazu, Hosomizu, Kohei, Miyasaka, Hiroshi, Imahori, Hiroshi, Nakashima, Satoru
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 29.09.2006
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2006.07.082

Ultrafast electron transfer in a porphyrin-ferrocene dyad was studied by femtosecond up-conversion and pump–probe methods. Vibrational coherence of four modes in the pump–probe data was analyzed, and a shift of vibrational phase was found for selected modes associated to the translation and rotation of ferrocene relative to the porphyrin plane. Ultrafast electron transfer in a porphyrin-ferrocene dyad in which the ferrocene moiety is directly linked at the meso-position of the porphyrin was studied using femtosecond up-conversion and pump–probe techniques. The time constant of electron transfer was ∼110 fs both in benzene and tetrahydrofuran. Vibrational coherence of the 130-, 200-, and 250-cm −1 modes, which were assigned to the translation and rotation of ferrocene, was observed, and was found to be phase shifted with respect to the vibrational coherence of the 330-cm −1 mode. The relation between this behavior of vibrational modes and electron transfer is discussed.