Comparative photophysical properties of free-base, bis-Zn(II), bis-Cu(II), and bis-Co(II) doubly N-confused hexaphyrins(1.1.1.1.1.1)

Dongho Kim, Jung Ho Kwon, Tae Kyu Ahn, Min Chul Yoon, Deok Yun Kim, Mi Kyoung Koh, Hiroyuki Furuta, Masaakl Suzuki, Atsuhiro Osuka

    研究成果: Contribution to journalArticle査読

    33 被引用数 (Scopus)

    抄録

    We have comparatively investigated the photophysics of a series of bis-metal doubly N-confused hexaphyrins(1.1.1.1.1.1) using time-resolved fluorescence, femtosecond transient absorption, two-photon absorption measurements, and geometry-optimized ab initio calculations. Bis-Zn(II) and free-base doubly N-confused hexaphyrins exhibit well-resolved and red-shifted B- and Q-like absorption bands compared with porphyrins. Their allowed transitions are (π,π*) transitions of the hexaphyrin ring, as confirmed by the HOMO and LUMO frontier orbitals based on ab initio calculations at the B3LYP/6-31G level. On the other hand, the absorption spectra of bis-Cu(II) and bis-Co(II) doubly N-confused hexaphyrins are relatively broad, presumably due to large couplings between the metal d-orbitals and π-electrons of the hexaphyrin ring. Owing to these couplings, bis-Cu(II) and bis-Co(II) doubly N-confused hexaphyrins have much shorter excited-state lifetimes of 9.4 ± 0.3 ps and 670 fs, respectively, than those (267 ± 16 and 62.4 ± 1.2 ps, respectively) of bis-Zn(II) and free-base doubly N-confused hexaphyrins. The two-photon absorption cross section (σ(2)) values, which are believed to depend strongly on the ring planarity (π-conjugation), are in line with the excited-state lifetime trends.

    本文言語英語
    ページ(範囲)11683-11690
    ページ数8
    ジャーナルJournal of Physical Chemistry B
    110
    24
    DOI
    出版ステータス出版済み - 6 22 2006

    All Science Journal Classification (ASJC) codes

    • 物理化学および理論化学
    • 表面、皮膜および薄膜
    • 材料化学

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