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Lanthanide Luminescence Thermometry and Slow Magnetic Relaxation in 3-D Polycyanidometallate-Based Materials
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-11-08 , DOI: 10.1021/acs.inorgchem.2c03128 Konstantinos Karachousos-Spiliotakopoulos 1 , Vassilis Tangoulis 1 , Nikos Panagiotou 2 , Anastasios Tasiopoulos 2 , Vassilis Nastopoulos 1 , Eufemio Moreno-Pineda 3 , Wolfgang Wernsdorfer 4, 5 , Michael Schulze 5 , Alexandre M P Botas 6, 7 , Luis D Carlos 6
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-11-08 , DOI: 10.1021/acs.inorgchem.2c03128 Konstantinos Karachousos-Spiliotakopoulos 1 , Vassilis Tangoulis 1 , Nikos Panagiotou 2 , Anastasios Tasiopoulos 2 , Vassilis Nastopoulos 1 , Eufemio Moreno-Pineda 3 , Wolfgang Wernsdorfer 4, 5 , Michael Schulze 5 , Alexandre M P Botas 6, 7 , Luis D Carlos 6
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Two three-dimensional (3-D) polycyanidometallate-based luminescent thermometers with the general formula {Ln4Co4(CN)24(4-benpyo)17(H2O)·7H2O}n Ln = (Dy(III)(1), Eu(III)(2)), based on the red-emissive diamagnetic linker [Co(CN)6]3– and the bulky pyridine derivative that possesses the N-oxide moiety, 4-benzyloxy-pyridine N-oxide (benpyo), were prepared for the first time. The structure of compound 1 has been determined by single-crystal X-ray crystallography while the purity and structure of 2 have been confirmed by CHN, Fourier transform infrared spectroscopy (FT-IR), and powder X-ray diffraction (PXRD) analysis. Magnetic AC susceptibility measurements at zero field show no single-molecule magnet (SMM) behavior indicating fast relaxation operating in 1. Upon application of an optimal field of 2 kOe, the SMM character of compound 1 is revealed while the τ(Τ) can be reproduced solely considering the Raman process τ–1 = CTn with C = 7.0901(3) s–1 K–n and n = 3.58(1), indicating that a high density of low-lying states and optical as well as acoustic phonons play a major role in the relaxation mechanism. Micron-sized superconducting quantum interference device (μ-SQUID) loops show a very narrow opening in agreement with the AC susceptibility studies and complete active space self-consistent field (CASSCF) calculations. The interaction operating between the Dy(III) ions was quantified from CASSCF calculations. Good agreement is found by fitting the experimental DC χMΤ(Τ) and M(H), employing the Lines model, with JLines = −0.087 cm–1 (−0.125 K). The excitation spectra of compound 2 are used for temperature sensing in the 25–325 nm range with a maximum relative thermal sensitivity, Sr = 0.6% K–1 at 325 K, whereas compound 1 operates as a luminescent thermometer based on its emission features in the temperature range of 16–350 K with Sr ≈ 2.3% K–1 at 240 K.
中文翻译：
3-D 多氰基金属酸盐基材料中的镧系元素发光测温和慢磁弛豫
两个三维 (3-D) 多氰基金属酸盐基发光温度计，通式为 {Ln 4 Co 4 (CN) 24 (4-benpyo) 17 (H 2 O)·7H 2 O} n Ln = (Dy(III )( 1 ), Eu(III)( 2 )), 基于红光发射抗磁连接体 [Co(CN) 6 ] 3–和具有 N-氧化物部分的庞大吡啶衍生物 4-苄氧基-吡啶 N -氧化物（benpyo），是第一次制备。化合物1的结构已通过单晶 X 射线晶体学确定，而2的纯度和结构已通过 CHN、傅里叶变换红外光谱 (FT-IR) 和粉末 X 射线衍射 (PXRD) 分析证实。零场下的交流磁化率测量显示没有单分子磁体 (SMM) 行为表明1中的快速弛豫操作。在应用 2 kOe 的最佳场时，化合物1的 SMM 特征被揭示，而 τ( Τ ) 可以仅考虑拉曼过程 τ –1 = CT n和C = 7.0901(3) s –1 K – n和n= 3.58(1)，表明高密度的低位态和光学以及声学声子在弛豫机制中起着重要作用。微米大小的超导量子干涉装置 (μ-SQUID) 环路显示出一个非常窄的开口，这与 AC 磁化率研究和完整的活性空间自洽场 (CASSCF) 计算一致。Dy(III) 离子之间的相互作用通过 CASSCF 计算进行量化。通过拟合实验性 DC χ M Τ ( Τ ) 和M ( H )，采用线模型，J线= −0.087 cm –1 (−0.125 K)，可以找到良好的一致性。化合物2的激发光谱用于 25–325 nm 范围内的温度传感，具有最大相对热灵敏度，在 325 K 时S r = 0.6% K –1，而化合物1根据其在 16 的温度范围内的发射特性用作发光温度计–350 K ，240 K 时S r ≈ 2.3% K –1 。
更新日期：2022-11-08
中文翻译：
3-D 多氰基金属酸盐基材料中的镧系元素发光测温和慢磁弛豫
两个三维 (3-D) 多氰基金属酸盐基发光温度计，通式为 {Ln 4 Co 4 (CN) 24 (4-benpyo) 17 (H 2 O)·7H 2 O} n Ln = (Dy(III )( 1 ), Eu(III)( 2 )), 基于红光发射抗磁连接体 [Co(CN) 6 ] 3–和具有 N-氧化物部分的庞大吡啶衍生物 4-苄氧基-吡啶 N -氧化物（benpyo），是第一次制备。化合物1的结构已通过单晶 X 射线晶体学确定，而2的纯度和结构已通过 CHN、傅里叶变换红外光谱 (FT-IR) 和粉末 X 射线衍射 (PXRD) 分析证实。零场下的交流磁化率测量显示没有单分子磁体 (SMM) 行为表明1中的快速弛豫操作。在应用 2 kOe 的最佳场时，化合物1的 SMM 特征被揭示，而 τ( Τ ) 可以仅考虑拉曼过程 τ –1 = CT n和C = 7.0901(3) s –1 K – n和n= 3.58(1)，表明高密度的低位态和光学以及声学声子在弛豫机制中起着重要作用。微米大小的超导量子干涉装置 (μ-SQUID) 环路显示出一个非常窄的开口，这与 AC 磁化率研究和完整的活性空间自洽场 (CASSCF) 计算一致。Dy(III) 离子之间的相互作用通过 CASSCF 计算进行量化。通过拟合实验性 DC χ M Τ ( Τ ) 和M ( H )，采用线模型，J线= −0.087 cm –1 (−0.125 K)，可以找到良好的一致性。化合物2的激发光谱用于 25–325 nm 范围内的温度传感，具有最大相对热灵敏度，在 325 K 时S r = 0.6% K –1，而化合物1根据其在 16 的温度范围内的发射特性用作发光温度计–350 K ，240 K 时S r ≈ 2.3% K –1 。
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