The optical thermometer has shown great promise for use in the fields of aeronautical engineering, environmental monitoring and medical diagnosis. Self-referencing lanthanide thermo-probes distinguish themselves because of their accuracy, calibration, photostability, and temporal dimension of signal. However, the use of conventional lanthanide-doped materials is limited by their poor reproducibility, random distance between energy transfer pairs and interference by energy migration, thereby restricting their utility. Herein, a strategy for synthesizing hetero-dinuclear complexes that comprise chemically similar lanthanides is introduced in which a pair of thermosensitive dinuclear complexes, cycTb-phEu and cycEu-phTb, were synthesized. Their structures were geometrically optimized with an internuclear distance of approximately 10.6Å. The sensitive linear temperature-dependent luminescent intensity ratios of europium and terbium emission over a wide temperature range (50-298K and 10-200K, respectively) and their temporal dimension responses indicate that both dinuclear complexes can act as excellent self-referencing thermometers. The energy transfer from Tb³⁺ to Eu³⁺ is thermally activated, with the most important pathway involving the ⁷F₁ Eu³⁺J-multiplet at room temperature. The energy transfer from the antenna to Eu³⁺ was simulated, and it was found that the most important ligand contributions to the rate come from transfers to the Eu³⁺ upper states rather than direct ligand-metal transfer to ⁵D₁ or ⁵D₀. As the first molecular-based thermometer with clear validation of the metal ratio and a fixed distance between the metal pairs, these dinuclear complexes can be used as new materials for temperature sensing and can provide a new platform for understanding the energy transfer between lanthanide ions.

中文翻译：

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化学计量的-二联分子温度计：能量传递特性。

光学温度计已显示出在航空工程，环境监测和医学诊断领域的广阔前景。自引用镧系元素热探针因其准确性，校准，光稳定性和信号的时间维度而与众不同。然而，常规的掺杂镧系元素的材料的可再现性差，能量转移对之间的随机距离以及能量迁移的干扰限制了它们的使用，从而限制了它们的实用性。在本文中，引入了用于合成包含化学上相似的镧系元素的杂-核复合物的策略，其中合成了一对热敏性双核复合物cycTb-phEu和cycEu-phTb。它们的结构经过几何优化，核间距约为10.6Å。a和ter在宽温度范围内（分别为50-298K和10-200K）的灵敏线性温度依赖性发光强度比及其时间尺度响应表明，两种双核配合物均可作为出色的自参考温度计。来自Tb的能量转移³⁺到Eu ³⁺被热激活，最重要的途径是在室温下⁷ F ₁ Eu ³⁺ J -multiplet。模拟了从天线到Eu ³⁺的能量转移，发现对速率最重要的配体贡献来自于向Eu ³⁺上层态的转移，而不是直接由配体-金属转移至⁵ D ₁或⁵ D ₀。作为第一个基于分子的温度计，其金属比和金属对之间的固定距离均得到明确验证，这些双核配合物可以用作温度感测的新材料，并且可以为了解镧系元素离子之间的能量转移提供新的平台。