中国科学院福建物质结构研究所林华团队报道了[Cs₁₄Cl][Tm₇₁Se₁₁₀]——一种不寻常的含有不同价Tm中心和超低导热性的盐包体硫族化合物。相关研究成果于2024年7月29日发表在《结构化学》。

盐包合硫族化合物（SICs）作为一类新兴的无机杂化材料，因其独特的主客体结构特征和在光电子领域的出色性能，在过去十年中受到了广泛关注。

该文中，研究人员使用适当的通量方法发现了一种新的四元SIC[Cs₁₄Cl][Tm₇₁Se₁₁₀]。该结构在晶格中由两个不同的部分组成：主体[Tm₇₁Se₁₁₀]^13-骨架和客体[Cs₁₄Cl]¹³⁺聚阳离子。值得注意的是，这种结构首次揭示了混合价Tm²⁺/Tm³⁺和不同类型封闭腔的存在。

此外，热传输性能测试表明，在323至673 K的温度范围内，它具有0.29至0.24 W/mK的超低导热性。该值是多晶硫属化物中报告的最低值之一。

该项研究不仅推进了稀土基化合物的配位化学，还重申了SIC半导体是实现超低导热性的有前景的体系。

附：英文原文

Title: [Cs14Cl][Tm71Se110]: An unusual salt-inclusion chalcogenide containing different valent Tm centers and ultralow thermal conductivity

Author: Hong Chen, Mao-Yin Ran, Long-Hua Li, Xin-Tao Wu, Hua Lin

Issue&Volume: 2024-07-29

Abstract: As an emerging class of inorganic hybrid materials, salt-inclusion chalcogenides (SICs) have garnered significant attention in the past decade owing to their distinct host-guest structural characteristics and outstanding performance in the field of optoelectronics. In this study, a novel quaternary SIC [Cs14Cl][Tm71Se110] has been discovered using an appropriate flux method. The structure comprises two distinct parts within the lattice: the host [Tm71Se110]13– framework and the guest [Cs14Cl]13+ polycation. Notably, this structure reveals the presence of mixed-valent Tm2+/Tm3+ and different types of closed cavities for the first time. Additionally, thermal transport performance testing shows that it has ultralow thermal conductivity, ranging from 0.29 to 0.24 W/mK, within the temperature range of 323 to 673 K. This value is one of the lowest reported values among polycrystalline chalcogenides. This research not only advances the coordination chemistry of rare-earth-based compounds but also reaffirms that SIC semiconductors are promising systems for achieving ultralow thermal conductivity.

DOI: 10.1016/j.cjsc.2024.100397

Source: http://cjsc.ac.cn/cms/issues/667