Ratiometric Raman and Luminescent Thermometers Constructed from Dysprosium Thiocyanidometallate Molecular Magnets
Ratiometric Raman and Luminescent Thermometers Constructed from Dysprosium Thiocyanidometallate Molecular Magnets
复制标题
DOI：
10.1002/adom.202201675
复制
发表时间：
2022-09
影响因子：
9
通讯作者：
Kunal Kumar;O. Stefańczyk;S. Chorazy;K. Nakabayashi;S. Ohkoshi
中科院分区：
文献类型：
--
作者：
Kunal Kumar;O. Stefańczyk;S. Chorazy;K. Nakabayashi;S. Ohkoshi
分子晶体作为温度传感器，设计用于多种测量技术，是一种很有前途的自校准温度计的途径。报道了含有弱键合稀土(III)和Au(I)金属络合物的分子组装[DyxIIIY1–xIII(phen)2(μ‐OH)2(H2O)2]·[AuI(SCN)2]2·phen·0.5MeCN·0.5H2O(x=0，0.1，0.02；phen=1，10-邻菲咯啉)。它们在具有尖峰的低频(LF)区域有拉曼散射，这是设计拉曼温度计的先决条件之一。用三个振动带表征了拉曼测温行为，并比较了它们的热灵敏度和发射测温能力。与Au···Au振动有关的低频声子有助于提高发射温度计和拉曼温度计的温度灵敏度。此外，还制备了同时含有Dy3+和Y3+离子的磁性稀释络合物，通过拉曼光谱和发射光谱验证了等结构混合金属材料的温度传感能力。化合物浸泡在各种台式溶剂中，以揭示拉曼温度计的坚固性和功能。此外，它们还揭示了单分子磁特性，揭示了低频声子对自旋弛豫过程的影响。因此，已报道的分子材料是拉曼和发光温度计，它们包含一个分子磁中心，硫氰酸根离子因其发射和拉曼活性而起着关键作用。
Molecular crystals acting as temperature sensors, designed for multiple measurement techniques, can be a promising pathway for self‐calibrating thermometers. The molecular assemblies [DyxIIIY1–xIII(phen)2(μ‐OH)2(H2O)2]·[AuI(SCN)2]2·phen·0.5MeCN·0.5H2O (x = 0, 0.1, 0.02; phen = 1,10‐phenanthroline) which contain weakly bonded lanthanide(III) and Au(I) metal complexes are reported. They have Raman scattering in the low‐frequency (LF) region with sharp peaks, one of the prerequisites to design Raman thermometers. The Raman thermometric behaviors are characterized by three vibrational bands, and their thermal sensitivity is compared with their emission thermometric ability. The LF phonon linked with the Au···Au vibration helps increase the thermometric sensitivity of emission and Raman thermometers. Additionally, magnetically diluted complexes containing both Dy3+ and Y3+ ions are prepared to demonstrate the effect of temperature sensing capability through Raman and emission spectroscopy among isostructural mixed‐metal materials. Compounds are immersed inside various benchtop solvents to unravel the robustness and functioning of Raman thermometers. Furthermore, they reveal single‐molecule magnet properties, which disclose the effect of LF phonons on the spin relaxation process. Therefore, the reported molecular materials are Raman and luminescent thermometers, and they contain a molecular magnetic center with thiocyanidoaurate ions playing a critical role due to their emissive and Raman activities.