多功能手性双核DyIII对映体：具有很强的三次谐波产生响应的单分子磁铁行为

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure Pub Date : 2025-04-19 DOI:10.1016/j.molstruc.2025.142445

Rong-Min Wei , Hui Hu , Min Yang , Da-Shuai Zhang , Dunqing Wang , Chunxiao Jia , Fengcai Li , Xi-Li Li , Cai-Ming Liu

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引用次数: 0

摘要

利用前体Dy(tta)3(H2O)2与对映纯双齿n给体（LR/LS）分别以2:1的化学量比反应，得到了一对手性双核DyIII对映体[Dy2(tta)6(LR)]·0·5H2O （D-1）和[Dy2(tta)6(LS)]·0·5H2O (L-1)，并进行了结构表征，其中Htta = 4,4,4-三氟-1-（2-噻吩基）-1,3-丁二酮，LR/LS =(-)/(+)-2,5-双（4 ',5 ' -蒎烯-2 ' -吡啶基）吡嗪。它们不仅在零直流场下表现出单分子磁体（SMM）行为，而且同时表现出二次谐波和三次谐波（SHG和THG）响应。更值得注意的是，D-1/L-1的THG强度非常强（高达375/350 × α-SiO2），分别是唯一THG活性的Dy(tta)3(H2O)2 （29 × α-SiO2）的13倍和12倍。这表明，在Dy(tta)3(H2O)2中引入具有大π共轭体系的LR和LS对称分子结构，不仅可以引起SHG响应的发生，而且可以显著提高THG性能。

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Multifunctional chiral dinuclear DyIII enantiomeric pairs: showing single-molecule magnet behaviors with very strong third-harmonic generation responses

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Multifunctional chiral dinuclear DyIII enantiomeric pairs: showing single-molecule magnet behaviors with very strong third-harmonic generation responses

Using the precursor Dy(tta)₃(H₂O)₂ to react with enantiopure bis-bidentate N-donors (L_R/L_S) at a 2:1 stoichiometric ratio, respectively, a pair of chiral dinuclear Dy^III enantiomers formulated as [Dy₂(tta)₆(L_R)]·0_·5H₂O (D-1) and [Dy₂(tta)₆(L_S)]·0_·5H₂O (L-1) were attained and structurally characterized, in which Htta = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione and L_R/L_S = (-)/(+)-2,5-bis(4′,5′-pinene-2′-pyridyl)pyrazine. They not only show single-molecule magnet (SMM) behaviors at a zero dc field but also display simultaneously second- and third-harmonic generation (SHG and THG) responses. More notably, the THG intensities of D-1/L-1 are very strong (as high as 375/350 × α-SiO₂), which are 13 and 12 times larger than that of the only THG-active Dy(tta)₃(H₂O)₂ (29 × α-SiO₂), respectively. This finding indicates that introducing L_R and L_S bearing symmetric molecular structures with large π-conjugated systems into Dy(tta)₃(H₂O)₂ not only leads to the occurrence of the SHG response but also significantly enhances the THG performance.

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来源期刊

Journal of Molecular Structure 化学-物理化学

CiteScore

7.10

自引率

15.80%

发文量

2384

审稿时长

45 days

期刊介绍： The Journal of Molecular Structure is dedicated to the publication of full-length articles and review papers, providing important new structural information on all types of chemical species including: • Stable and unstable molecules in all types of environments (vapour, molecular beam, liquid, solution, liquid crystal, solid state, matrix-isolated, surface-absorbed etc.) • Chemical intermediates • Molecules in excited states • Biological molecules • Polymers. The methods used may include any combination of spectroscopic and non-spectroscopic techniques, for example: • Infrared spectroscopy (mid, far, near) • Raman spectroscopy and non-linear Raman methods (CARS, etc.) • Electronic absorption spectroscopy • Optical rotatory dispersion and circular dichroism • Fluorescence and phosphorescence techniques • Electron spectroscopies (PES, XPS), EXAFS, etc. • Microwave spectroscopy • Electron diffraction • NMR and ESR spectroscopies • Mössbauer spectroscopy • X-ray crystallography • Charge Density Analyses • Computational Studies (supplementing experimental methods) We encourage publications combining theoretical and experimental approaches. The structural insights gained by the studies should be correlated with the properties, activity and/ or reactivity of the molecule under investigation and the relevance of this molecule and its implications should be discussed.