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
麻秀芳 1秘鹏飞 1鲍松松 1郑丽敏1
作者信息
- 1. 南京大学化学化工学院,配位化学国家重点实验室,南京 210023
- 折叠
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.
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-faceπ-π interacted anthracene groups that meet the Schmidt rule for a[4+4]pho-tocycloaddition 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 reac-tion,accompanied by changes in their luminescence colors from yellow-green to blue.Furthermore,partial photocy-cloaddition of anthracene groups in 2Nd@Y led to a slight change in the magnetic dynamics,manifested by an in-crease 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.CCDC:2303850,1Er;2303856,2Nd;2303854,3Y.
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Key words
anthracene-based phosphonate complex/lanthanide single molecule magnet/photoluminescence/doping effect引用本文复制引用
基金项目
国家自然科学基金(22273037)
国家自然科学基金(21731003)
出版年
2024
NETL
NSTL
维普
万方数据