Structural Expansion and Enhanced Photocurrent Conversion of Selenido Stannates with Cu+ Ions.

IF 8.5 Q1 CHEMISTRY, MULTIDISCIPLINARY JACS Au Pub Date : 2024-09-25 eCollection Date: 2024-10-28 DOI:10.1021/jacsau.4c00375
Zhou Wu, Benjamin Peerless, Panpan Wang, Wolfgang Schuhmann, Stefanie Dehnen
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Abstract

As a means of tuning the electronic properties of tin-chalcogenide-based compounds, we present a strategy for the compositional and structural expansion of selenido stannate frameworks under mild conditions by introducing Cu+ ions into binary anionic Sn/Se aggregates in ionothermal reactions. The variable coordination modes of Cu+-contrasting with tetrahedral {SnSe4} or trigonal bipyramidal {SnSe5} units-and corresponding expansion toward ternary Cu/Sn/Se substructures helped to add another degree of freedom to the nanoarchitectures. As desired, the variation of the structural features was accompanied by concomitant changes of the physical properties. Upon treatment of alkali metal salts of the [SnSe4]4- anion at slightly elevated temperatures (120 or 150 °C) in ionic liquids, we isolated a series of compounds comprising ternary or quaternary cluster molecules or networks of cluster units, (C2C2Im)9Li[Cu10Sn6Se22] (1), (C2C2Im)4[Cu8Sn6Se18] (2), (C2C1Im)3[Cu5Sn3Se10] (3), and (C2C2Im)5[Cu8Sn6Se18F]·(C2C2Im)[BF4] (4; C2C2Im = 1,3-diethyl-imidazolium, C2C1Im = 1-ethyl-3-methyl-imidazolium), which were investigated in terms of their optical gaps and photocurrent conversion properties. As illustrated by the synthesis and characterization of an additional salt that does not include Cu+, {(C2C2Im)2[Sn3Se7]}4·{(C2C2Im)[BF4]}2 (5), the significant role of Cu+ in this system was shown to be 3-fold: (a) structural expansion, (b) narrowing of the optical gap, and (c) photocurrent enhancement. By this three-in-one effect, the work offers an in-depth understanding of chalcogenido metalate chemistry with atomic precision.

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硒基锡酸盐与 Cu+ 离子的结构扩展和光电流转换增强。
作为调整锡-卤化镓基化合物电子特性的一种方法,我们提出了一种策略,通过在离子热反应中将 Cu+ 离子引入二元阴离子锡/硒聚集体,在温和条件下扩展硒基锡酸酯框架的组成和结构。Cu+ 与四面体 {SnSe4} 或三叉双金字塔 {SnSe5} 单元的配位模式各不相同,相应地向三元 Cu/Sn/Se 子结构扩展,有助于为纳米结构增加另一种自由度。正如所期望的那样,结构特征的变化伴随着物理性质的相应变化。在离子液体中以略微升高的温度(120 或 150 °C)处理[SnSe4]4-阴离子的碱金属盐后,我们分离出一系列由三元或四元簇分子或簇单元网络组成的化合物、(C2C2Im)9Li[Cu10Sn6Se22] (1)、(C2C2Im)4[Cu8Sn6Se18] (2)、(C2C1Im)3[Cu5Sn3Se10] (3) 和 (C2C2Im)5[Cu8Sn6Se18F]-(C2C2Im)[BF4] (4);C2C2Im = 1,3-二乙基咪唑鎓,C2C1Im = 1-乙基-3-甲基咪唑鎓),研究了它们的光隙和光电流转换特性。通过合成和表征不含 Cu+ 的附加盐 {(C2C2Im)2[Sn3Se7]}4-{(C2C2Im)[BF4]}2 (5),证明了 Cu+ 在该体系中的三重重要作用:(a) 结构扩展;(b) 光隙缩小;(c) 光电流增强。通过这种三合一效应,该研究成果以原子精度深入理解了钙基金属酸盐化学。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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10 weeks
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