Transition metal chalcogenophosphates have garnered extensive attention owing to their diverse array of optical and magnetic properties. However, one of the less explored members within this family is CoPS₃, largely due to the time-intensive nature of its solid-state synthesis preparation. In this study, we present an ion exchange metathesis methodology to address these challenges. Through the exploitation of the versatile thiophosphate motif, we have successfully synthesized CoPS₃ by reacting isostructural MgPS₃ with CoCl₂. Our findings from ex situ investigations highlight a correlation between the degree of structural disorder and the concentration of CoCl₂, impacting not only the bulk magnetism but also the observed phonon modes, as evidenced by magnetic susceptibility and Raman spectroscopy, respectively. This structural disorder seemingly plays a pivotal role in shaping the mechanism underlying the formation of CoPS₃ through the metathesis approach, which we comprehensively elucidate using in situ synchrotron powder X-ray diffraction. Our detailed analysis uncovers a two-step progression in the metathesis reaction involving ion diffusion kinetics and grain boundary melt phenomena. These insights not only enhance our understanding of the reaction dynamics but also pave the way for refining and optimizing the synthesis of such compounds with the desired structures and properties.

中文翻译：

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硫代磷酸钴离子交换复分解的动力学和热力学途径


过渡金属硫属磷酸盐由于其多样化的光学和磁性特性而受到广泛关注。然而，该家族中较少被研究的成员之一是 CoPS ₃ ，这主要是由于其固态合成制备的时间密集性。在这项研究中，我们提出了一种离子交换复分解方法来应对这些挑战。通过利用通用的硫代磷酸基序，我们通过同构 MgPS ₃ 与 CoCl ₂ 反应成功合成了 CoPS ₃ 。我们的异位研究结果强调了结构无序程度与 CoCl ₂ 浓度之间的相关性，不仅影响体磁性，还影响观察到的声子模式，如磁化率和拉曼光谱所证明的那样，分别。这种结构紊乱似乎在通过复分解方法塑造 CoPS ₃ 形成机制方面发挥着关键作用，我们利用原位同步加速器粉末 X 射线衍射全面阐明了这一机制。我们的详细分析揭示了涉及离子扩散动力学和晶界熔化现象的复分解反应的两步进展。这些见解不仅增强了我们对反应动力学的理解，而且为改进和优化具有所需结构和性质的此类化合物的合成铺平了道路。