Pyrolysis of Helical Coordination Polymers for Metal-Sulfide-Based Helices with Broadband Chiroptical Activity
Pyrolysis of Helical Coordination Polymers for Metal-Sulfide-Based Helices with Broadband Chiroptical Activity
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DOI：
10.1021/acsnano.7b00103
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发表时间：
2017-06-01
期刊：
影响因子：
17.1
通讯作者：
Sada, Kazuki
中科院分区：
文献类型：
--
作者：
Hirai, Kenji;Yeom, Bongjun;Sada, Kazuki
在可见光区具有宽带响应的手光材料的制备是充分实现其潜在应用的关键。实现宽带手性活性的一种方法是从在可见光区域中表现出宽带吸收的材料制造手性纳米结构。然而，用于手性材料的化合物主要限于具有窄带光谱响应的材料。在这里，我们合成了基于Ag 2S的纳米螺旋衍生自螺旋配位聚合物。作为前体的右手和左手配位螺旋是由L-和D-谷胱甘肽与Ag+和少量Cu 2+制备的。热解的配位螺旋产生的右手和左手螺旋的Cu0.12Ag1.94S/C，表现出手性活性跨越整个可见光区。有限元法模拟证实了宽带手性活性归因于协同的宽带光吸收和光散射。此外，以D-谷氨酸-半胱氨酸为原料，合成了另一系列Cu_（0.10）Ag_（1.90）S/C纳米螺旋。纳米螺旋的螺距长度通过改变肽来控制，这改变了它们的手性性质。配位螺旋的热解使人们能够制造基于Ag 2S的螺旋材料，其能够实现宽带手性光学活性，但由于缺乏合成路线而尚未被探索。
Fabrication of chiroptical materials with broadband response in the visible light region is vital to fully realize their potential applications. One way to achieve broadband chiroptical activity is to fabricate chiral nanostructures from materials that exhibit broadband absorption in the visible light region. However, the compounds used for chiroptical materials have predominantly been limited to materials with narrowband spectral response. Here, we synthesize Ag2S-based nanohelices derived from helical coordination polymers. The right- and left-handed coordination helices used as precursors are prepared from L- and D-glutathione with Ag+ and a small amount of Cu2+. The pyrolysis of the coordination helices yields right- and left-handed helices of Cu0.12Ag1.94S/C, which exhibit chiroptical activity spanning the entire visible light region. Finite element method simulations substantiate that the broadband chiroptical activity is attributed to synergistic broadband light absorption and light scattering. Furthermore, another series of Cu0.10Ag1.90S/C nanohelices are synthesized by choosing the or D-Glu-Cys as starting materials. The pitch length of nanohelicies is controlled by changing the peptides, which alters their chiroptical properties. The pyrolysis of coordination helices enables one to fabricate helical Ag2S-based materials that enable broadband chiroptical activity but have not been explored owing to the lack of synthetic routes.