Cs₃W₃PO₁₃: A Tungsten Phosphate with One-Dimensional Zigzag Tunnels Exhibiting Strongly Anisotropic Thermal Expansion

A new tungsten phosphate, Cs3W3PO13, is synthesized using the high-temperature flux method. Cs3W3PO13 crystallizes in the space group Pnma and contains one-dimensional zigzag tunnels, which are found for the first time in tungsten phosphate. This highly anisotropic structural feature results in a very strong anisotropic thermal expansion, with thermal expansion coefficients of 14.15 ± 1.11 and 0.72 ± 0.22 M K–1 along the a and b axes, respectively, over the temperature range from 13 to 270 K. In addition, thermal analysis, UV–vis–near-IR diffuse reflectance, and first-principles electronic structure calculations on Cs3W3PO13 are performed.本研究采用高温熔剂法合成了一种新型磷酸钨化合物Cs₃W₃PO₁₃。该化合物以空间群Pnma结晶，其结构中存在一维之字形隧道，这类隧道在磷酸钨体系中尚属首次报道。这种高度各向异性的结构特征使其表现出极强的各向异性热膨胀行为：在13 K至270 K的温度区间内，其沿a轴和b轴的热膨胀系数分别为14.15 ± 1.11和0.72 ± 0.22 M·K⁻¹。此外，本研究还对Cs₃W₃PO₁₃开展了热分析、紫外-可见-近红外漫反射光谱表征以及第一性原理电子结构计算。