Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (22): 2306-2310.DOI: 10.6023/A12090687 Previous Articles     Next Articles

Communications

三联吡啶锇Os(Ⅱ)配合物为光敏剂的二元铁氢化酶模拟化合物的合成及其光物理过程

王锋, 梁文静, 王文光, 陈彬, 冯科, 张丽萍, 佟振合, 吴骊珠   

  1. 中国科学院光化学转换与功能材料重点实验室 中国科学院理化技术研究所 北京 100190
  • 投稿日期:2012-09-19 发布日期:2012-10-18
  • 通讯作者: 吴骊珠 E-mail:lzwu@mail.ipc.ac.cn
  • 基金资助:
    项目受国家科技部(Nos. 2009CB22008, 2013CB834505)、国家自然科学基金(Nos. 21090343, 21002108, 20973189, 50973125, 91027041)和中国科学院知识创新工程(No. KGCX2-EW-311-1)资助.

Bis-terpyridine Os(Ⅱ) Complex Sensitized [FeFe] Hydrogenase Mimic Systems: Synthesis and Photophysical Study

Wang Feng, Liang Wen-Jing, Wang Wen-Guang, Chen Bin, Feng Ke, Zhang Li-Ping, Tung Chen-Ho, Wu Li-Zhu   

  1. Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190
  • Received:2012-09-19 Published:2012-10-18
  • Supported by:
    Project supported by the Ministry of Science and Technology of China (Nos. 2009CB22008, 2013CB834505), the National Science Foundation of China (Nos. 21090343, 21002108, 20973189, 50973125, 91027041), and the Knowledge Innovation Program of the Chinese Academy of Sciences (No. KGCX2-EW-311-1).

To mimic [FeFe] hydrogenase in nature, a PS-Fe2S2 type molecular dyad 1a and corresponding intermolecular model compounds 1b and 2 were synthesized and characterized. In the case of 1a, bis-terpyridine osmium(Ⅱ) complex as photosensitizer (PS) is covalently linked to a Fe2S2 cluster of [FeFe] hydrogenase mimic active site by a cyanide group. UV-Vis absorption spectrum revealed that both compounds 1a and 1b show two LC absorptions at the range of 280~330 nm, and 1MLCT absorption at ca. 498 nm. Particularly, 3MLCT absorption at 669 nm was clearly observed in compound 1b. Redox property of 1a and 1b was studied by cyclic voltammetry. Compound 1b shows two reduction potentials E(Os+2/+1) and E(Os+1/0) at -1.60 and -1.87 eV, and one oxidation potential E(Os+2/+3) at 0.51 eV. As compared with 1b, 1a shifts to more negative reduction potentials E(Os+2/+1) and E(Os+1/0) at -1.63 and -1.91 eV, respectively, but to more positive oxidation potential E(Os+2/+3) at 0.58 eV. Compound 1a also show an irreversible reduction potential of FeIFeI→FeIFe0 at -1.77 eV, which shifts 180 mV more negative than the corresponding reduction potential of compound 2. Excitation of the MLCT absorption of compound 1b leads to a strong luminescence at 740 nm with lifetime of 105 ns in CH3CN. However, the luminescence of dyad 1a was significantly quenched with efficiency of 92%. Under the same condition, the luminescence of 1b was slightly quenched by one equivalent of compound 2. The quenching efficiency of 1b was changed from 4% to 65% when the concentration of 2 was increased from 1 to 10 equivalents. According to Rehm-Weller equation, the photoinduced electron transfer from the excited osmium complex to Fe2S2 moiety neither in intramolecular dyad 1a nor in intermolecular (1b+2) system is feasible for the uphill free energy change. Consequently, the luminescence quenching in intramolecular dyad 1a and intermolecular (1b+2) system was tentatively attributed to energy transfer from 3MLCT of osmium complex to Fe2S2 cluster.

Key words: [FeFe] hydrogenase, osmium(Ⅱ) bis-terpyridine complex, electron transfer, energy transfer