2013年5月
Supramolecular Control of the Spin-Dependent Dynamics of Long-Lived Charge-Separated States at the Micellar Interface As Studied by Magnetic Field Effect
JOURNAL OF PHYSICAL CHEMISTRY B
- 巻
- 117
- 号
- 21
- 開始ページ
- 6443
- 終了ページ
- 6454
- 記述言語
- 英語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1021/jp401725f
- 出版者・発行元
- AMER CHEMICAL SOC
Spin selectivity in long-lived charge separation at the micellar interface is studied using the magnetic field effect (MFE). An amphiphilic viologen is complexed with a nonionic surfactant to form a supramolecular acceptor cage, of which the size is controlled by the acceptor concentration, as confirmed by dynamic light scattering measurement. Photoinduced electron transfer (ET) from a guest polyaromatic molecule to the viologen moiety is observed spin-dependently with time-resolved fluorescence (trFL) and transient absorption (TA). A negative MFE on the radical yield is successfully observed, which indicates generation of singlet-born long-lived radical pair that is realized by supramolecular control of the donor-acceptor (D-A) distances. The dominance of the singlet-precursor MFE is sensitive to the acceptor concentration, which presumably affects the D-A distance as well as the cage size. However, theoretical analysis of the MFE gives large recombination rates of ca. 10(8) s(-1), which indicate the contribution of spin-allowed recombination of the pseudocontact radical pair generated by still active in-cage diffusion. Dependence of the viologen concentration and alkyl chain length on the recombination and escape dynamics is discussed in terms of precursor spin states and the microenvironments in the cage.
- リンク情報
- ID情報
-
- DOI : 10.1021/jp401725f
- ISSN : 1520-6106
- Web of Science ID : WOS:000319896800011