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

作　　者：麻秀芳 秘鹏飞 鲍松松 郑丽敏 MA Xiufang;MI Pengfei;BAO Songsong;ZHENG Limin(State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Collaborative Innovation Centre of Advanced Microstructures,Nanjing University,Nanjing 210023,China)

机构地区：[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

出　　处：《无机化学学报》2024年第1期270-280,共11页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.22273037,21731003)资助。

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)(NO_(3))(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)(NO_(3))(depma_(2))(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Er~Ⅲ或Nd~Ⅲ掺杂到3Y晶格中,得到同构配合物Ln_(0.1)Y_(0.9)(SCN)_(2)(NO_(3))(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。Combining photoreactive anthracene moieties with lanthanide ions,we obtained three new isostructural mononuclear compounds with the formulas Ln(SCN)_(2)(NO_(3))(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-πinteracted 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,while3Ydisplays excimer emission in the visible region.As a result,only3Yunderwent photocycloaddition reaction under 395 nm UV light irradiation to form[Y(SCN)_(2)(NO_(3))(depma_(2))(4-hpy)_(2)]_n(3Y-UV).Magnetic studies revealed a field-induced slow relaxation of the magnetization at low temperatures for compounds1Erand2Nd,and the dominant relaxation process was the Raman process for 2Nd.After doping ErⅢor NdⅢinto3Y,we constructed the isomorphic samples Ln_(0.1)Y_(0.9)(SCN)_(2)(NO_(3))(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@Yled 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.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 

分 类 号：O614.344[理学—无机化学] O614.335[理学—化学] O614.322