| 掺杂对铒、钕蒽基配合物的光二聚反应及光磁性能调控的影响 |
| Effect of doping on the photodimerization reaction and the modulation of magneto-optical properties of erbium- and neodymium-anthracene complexes |
|
| 摘要: 选择具有光化学活性的蒽甲基膦酸二乙酯(depma)为配体、部分镧系离子为金属中心构筑了3例同构的单核配合物Ln (SCN)2(NO3)(depma)2(4-hpy)2(Ln=Er (1Er)，Nd (2Nd)，Y (3Y))，对其单分子磁体行为、发光性质和光二聚行为等进行了研究。荧光测试显示1Er和2Nd因配体到稀土离子的能量转移而显示近红外发光，但在可见光区无明显发光行为，同时不能发生光二聚反应。而3Y可以发射黄绿色荧光，并发生光二聚反应生成[Y (SCN)2(NO3)(depma2)(4-hpy)2]n(3Y-UV)。磁性测试显示1Er和2Nd在低温下均表现出场诱导的慢磁弛豫性质，其中2Nd的弛豫过程主要由拉曼过程主导。通过将ErⅢ或NdⅢ掺杂到3Y晶格中，得到同构配合物Ln0.1Y0.9(SCN)2(NO3)(depma)2(4-hpy)2(Ln=Er (1Er@Y)，Nd (2Nd@Y))，测试结果表明掺杂样品可以发生部分光二聚行为，同时伴随发光颜色的变化。此外，化合物2Nd@Y光反应前后磁性也发生了变化，拉曼过程的指数从3.8(2Nd@Y)提升到5.2(2Nd@Y-UV)，对应于光照前后晶格声子结构的变化。 |
| 关键词: 蒽基膦酸酯配合物 稀土单分子磁体 光致发光 掺杂效应 |
| 基金项目: 国家自然科学基金(No.22273037，21731003)资助。 |
| Abstract: Combining photoreactive anthracene moieties with lanthanide ions, we obtained three new isostructural mononuclear compounds with the formulas Ln(SCN)2(NO3)(depma)2(4-hpy)2 (Ln=Er (1Er), Nd (2Nd), Y (3Y), where depma is 9-diethylphosphonomethylanthracene, and their single molecule magnet and photodimerization behaviors were studied. All contain face-to-face π-π interacted anthracene groups that meet the Schmidt rule for a [4+4] photocycloaddition reaction. 1Er and 2Nd show characteristic near-infrared (NIR) luminescence owing to the efficient energy transfer from the ligand to the lanthanide ion, while 3Y displays excimer emission in the visible region. As a result, only 3Y underwent photocycloaddition reaction under 395 nm UV light irradiation to form [Y(SCN)2(NO3) (depma2)(4-hpy)2]n (3Y-UV). Magnetic studies revealed a field-induced slow relaxation of the magnetization at low temperatures for compounds 1Er and 2Nd, and the dominant relaxation process was the Raman process for 2Nd. After doping ErⅢ or NdⅢ into 3Y, we constructed the isomorphic samples Ln0.1Y0.9(SCN)2(NO3)(depma)2(4-hpy)2 (Ln= Er (1Er@Y), Nd (2Nd@Y)). Interestingly, the diluted samples exhibited an incomplete photocycloaddition reaction, accompanied by changes in their luminescence colors from yellow-green to blue. Furthermore, partial photocycloaddition of anthracene groups in 2Nd@Y led to a slight change in the magnetic dynamics, manifested by an increase in the n value of the Raman process from 3.8 (2Nd@Y) to 5.2 (2Nd@Y-UV) which is attributed to the change in its phonon structure. |
| Keywords: anthracene-based phosphonate complex lanthanide single molecule magnet photoluminescence doping effect |
| 投稿时间：2023-10-27 修订日期：2023-12-06 |
| 摘要点击次数: 4170 |
| 全文下载次数: 771 |
| 麻秀芳,秘鹏飞,鲍松松,郑丽敏.掺杂对铒、钕蒽基配合物的光二聚反应及光磁性能调控的影响[J].无机化学学报,2024,40(1):270-280. |
| 查看全文 查看/发表评论 下载PDF阅读器 |
| Support information: |
|
|
|
|
|
|
