Guest-Induced Two-Way Structural Transformation in a Layered Metal-Organic Framework Thin Film
Guest-Induced Two-Way Structural Transformation in a Layered Metal-Organic Framework Thin Film
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DOI：
10.1021/jacs.6b10913
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发表时间：
2016-12-28
影响因子：
15
通讯作者：
Kitagawa, Hiroshi
中科院分区：
文献类型：
--
作者：
Haraguchi, Tomoyuki;Otsubo, Kazuya;Kitagawa, Hiroshi
由金属有机框架（M0 F）制成的薄膜的制造已经被广泛地追求用于使用M0 F的结构响应的实际应用。然而，到目前为止，只有物理吸附引起的结构响应已在这些电影进行了研究。由于客体分子和主体MOFs中的活性金属位点之间形成键，化学吸附可以预期提供显著的结构响应。在这里，我们报告了化学吸附诱导的双向结构转变的纳米尺寸的MOF薄膜。我们采用分步法制备了二维层状结构的Fe[Pt（CN）（4）]薄膜。虽然合成后原样的膜显示出差的结晶度，但是该薄膜的脱水形式具有高度取向的结晶性质（膜-D），如通过同步加速器X射线衍射（XRD）所证实的。令人惊讶的是，在水和吡啶蒸气下，膜-D显示出化学吸附诱导的动态结构转变为Fe（L）（2）[Pt（CN）（4）]薄膜[L = H2O（膜-H），吡啶（膜-P）]，其中水和吡啶配位到开放的Fe 2+位点。动态结构转换也证实了原位XRD，吸附测量，红外反射吸收光谱。这是第一个报告的化学吸附诱导的动态结构响应的MOF薄膜，它提供了有用的见解，这将导致未来的实际应用的MOFs利用化学吸附诱导的结构响应。
Fabrication of thin films made of metal organic frameworks (MOFs) has been intensively pursued for practical applications that use the structural response of MOFs. However, to date, only physisorption-induced structural response has been studied in these films. Chemisorption can be expected to provide a remarkable structural response because of the formation of bonds between guest molecules and reactive metal sites in host MOFs. Here, we report that chemisorption-induced two-way structural transformation in a nanometer-sized MOF thin film. We prepared a two-dimensional layered-type MOF Fe[Pt(CN)(4)] thin film using a step-by-step approach. Although the as-synthesized film showed poor crystallinity, the dehydrated form of this thin film had a highly oriented crystalline nature (Film-D) as confirmed by synchrotron X-ray diffraction (XRD). Surprisingly, under water and pyridine vapors, Film-D showed chemisorption-induced dynamic structural transformations to Fe(L)(2)[Pt(CN)(4)] thin films [L = H2O (Film-H), pyridine (Film-P)], where water and pyridine coordinated to the open Fe2+ site. Dynamic structural transformations were also confirmed by in situ XRD, sorption measurement, and infrared reflection absorption spectroscopy. This is the first report of chemisorption-induced dynamic structural response in a MOF thin film, and it provides useful insights, which would lead to future practical applications of MOFs utilizing chemisorption-induced structural responses.