Oda Akira, Ohkubo Takahiro, Yumura Takashi, Kobayashi Hisayoshi, Kuroda Yasushige
Department of Chemistry, Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima, Kita-ku, Okayama 700-8530, Japan.
Dalton Trans. 2015 Jun 7;44(21):10038-47. doi: 10.1039/c5dt01088h.
Compared with mercury, the existence of Zn2 species is rare. We succeeded in preparing a stable Zn2 species by utilizing an MFI-type zeolite as a nano-reaction pot, which was confirmed using XAFS spectroscopy: the bands at R = 2.35 Å due to the Zn(+)-Zn(+) scattering and at 9660.7 eV due to the 1s-σ* (the anti-bonding orbital comprised of the 4s-4s orbital) transition of the Zn2 species. This species also gives the characteristic band around 42 000 cm(-1) due to its σ-σ* transition. Furthermore, UV-irradiation corresponding to the σ-σ* transition causes the bond dissociation, forming two unprecedented Zn(+) ions, and detached Zn(+) ions were recombined through heat-treatment at 573 K: [Zn(+)-Zn(+)] ⇄ 2Zn(+). These processes were reproduced by applying the DFT calculation method to the assumed triplet, σ(α)-σ*(α), structure formed on the M7-S2 site with the specific Al array in the MFI-type zeolite. Research into the specific field using zeolites to synthesize "ultra-state ions" is very promising.
与汞相比,Zn2物种的存在较为罕见。我们通过利用MFI型沸石作为纳米反应容器成功制备了一种稳定的Zn2物种,这一点通过XAFS光谱得以证实:由于Zn(+)-Zn(+)散射,在R = 2.35 Å处出现谱带,由于Zn2物种的1s-σ*(由4s-4s轨道组成的反键轨道)跃迁,在9660.7 eV处出现谱带。该物种由于其σ-σ跃迁,在42000 cm(-1)左右也给出特征谱带。此外,对应于σ-σ跃迁的紫外线照射会导致键解离,形成两个前所未有的Zn(+)离子,并且通过在573 K下进行热处理,分离出的Zn(+)离子会重新结合:[Zn(+)-Zn(+)] ⇄ 2Zn(+)。通过将DFT计算方法应用于在MFI型沸石中具有特定Al排列的M7-S2位点上形成的假定三重态σ(α)-σ*(α)结构,再现了这些过程。利用沸石合成“超态离子”的特定领域研究非常有前景。