Growing crystalline chalcogenidoarsenates in surfactants: from zero-dimensional cluster to three-dimensional framework.
Growing crystalline chalcogenidoarsenates in surfactants: from zero-dimensional cluster to three-dimensional framework.
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DOI：
10.1021/ja3116179
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发表时间：
2013-01
影响因子：
15
通讯作者：
Weiwei Xiong;E. Athresh;Y. Ng;J. Ding;Tom Wu;Qichun Zhang
中科院分区：
文献类型：
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作者：
Weiwei Xiong;E. Athresh;Y. Ng;J. Ding;Tom Wu;Qichun Zhang
虽然表面活性剂已被广泛用于调整纳米晶体的尺寸、形状和表面性质，并控制介孔骨架的孔径和物相，但使用表面活性剂作为反应介质来生长硫化物晶体是前所未有的。此外，与离子液体相比，表面活性剂价格便宜得多，可以具有多种功能，如酸性、碱性、中性、阳离子、阴离子，甚至嵌段。这些特征表明，表面活性剂有望成为开发新型硫系晶体的反应平台。在这项工作中，我们使用硫代砷盐作为模型系统来演示我们的策略。用三种不同的表面活性剂作为反应介质，得到了一系列从零维(0D)簇到三维(3D)骨架的新型硫代砷酸盐，即[NH(4)](8)[Mn(2)As(4)S(16)](1)，[Mn(NH(3))(6)][Mn(2)As(2)S(8)(N(2)H(4)(2)](2)，[ENH][Cu(3)As(2)S(5)](3)和[NH(4)][MNAs(3)S(6)](4)。1(0D)的带隙为2.31 eV，2(1D)为2.46 eV，3(2D)为1.91 eV，4(3D)为2.08 eV。4的磁学研究表明其具有微弱的反铁磁行为。我们的在表面活性剂中生长晶体材料的策略可以为制备具有不同结构和有趣性能的新型晶体材料提供令人兴奋的机会。
Although surfactants have been widely used to tailor the size, shape, and surface properties of nanocrystals and control the pore size and phases of mesoporous frameworks, the use of surfactants as reaction media to grow chalcogenide crystals is unprecedented. In addition, compared with ionic liquids, surfactants are much cheaper and can have multifunctional properties such as acidic, basic, neutral, cationic, anionic, or even block. These features suggest that surfactants could be promising reaction platforms for the development of novel chalcogenide crystals. In this work, we used chalcogenidoarsenates as a model system to demonstrate our strategy. By using three different surfactants as reaction media, we obtained a series of novel thioarsenates ranging from a zero-dimensional (0D) cluster to a three-dimensional (3D) framework, namely, [NH(4)](8)[Mn(2)As(4)S(16)] (1), [Mn(NH(3))(6)][Mn(2)As(2)S(8)(N(2)H(4))(2)] (2), [enH][Cu(3)As(2)S(5)] (3), and [NH(4)][MnAs(3)S(6)] (4). The band gaps (estimated from the steep absorption edges) were found to be 2.31 eV for 1 (0D), 2.46 eV for 2 (1D), 1.91 eV for 3 (2D), and 2.08 eV for 4 (3D). The magnetic study of 4 indicated weak antiferromagnetic behavior. Our strategy of growing crystalline materials in surfactants could offer exciting opportunities for preparing novel crystalline materials with diverse structures and interesting properties.