Wen He-Rui, Dong Piao-Ping, Liu Sui-Jun, Liao Jin-Sheng, Liang Fu-Yong, Liu Cai-Ming
School of Metallurgical and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, P.R. China.
Beijing National Laboratory for Molecular Sciences, Center for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P.R. China.
Dalton Trans. 2017 Jan 24;46(4):1153-1162. doi: 10.1039/c6dt04027f.
A new family of 3d-4f heterometallic trinuclear complexes, namely [MLnL]·2ClO·HO (HL = tris(((2-hydroxy-3-methoxybenzy1)amino)ethyl)amine, where M = Ni, Ln = Gd (1), Dy (2), and M = Zn, Ln = Gd (3), Dy (4)) were synthesized via the reaction of HL and Ln(NO)·6HO and Ni(ClO)·6HO or Zn(ClO)·6HO in a 2 : 1 : 2 ratio in the solution. Complexes 1-4 consisted of three metal ions arranged in an isosceles triangle manner. Magnetic properties investigations showed that complexes 1 and 2 exhibited weak ferromagnetic coupling between the Ni(ii) and Ln(iii) ions, whereas complex 4 displayed lanthanide single-ion magnetic properties. The alternating current (ac) magnetic susceptibilities of 4 revealed that both the in-phase (χ') and out-of-phase (χ'') signals are frequency- and temperature-dependent, which are typical features of the field-induced slow relaxation of the magnetization with U = 124.5 K. Complex 4 also exhibited an obvious butterfly-shaped hysteresis loop at 2 K, indicating that it is a single-ion magnet. Moreover, complex 4 showed stronger fluorescent emissions, which were typical narrow emission bands of lanthanide ions. Therefore, complex 4 can be considered as a molecular magnetic and luminescent material. Comparably, complex 2 showed very weak Dy-based emissions because the paramagnetic Ni ions quench the fluorescence and thereby lower the population of the triplet state.
合成了一个新的3d-4f异金属三核配合物家族,即[MLnL]·2ClO·HO(HL = 三[((2-羟基-3-甲氧基苄基)氨基)乙基]胺,其中M = Ni,Ln = Gd(1),Dy(2),以及M = Zn,Ln = Gd(3),Dy(4)),通过在溶液中以2∶1∶2的比例使HL与Ln(NO)·6HO和Ni(ClO)·6HO或Zn(ClO)·6HO反应得到。配合物1 - 4由以等腰三角形方式排列的三个金属离子组成。磁性研究表明,配合物1和2在Ni(ii)和Ln(iii)离子之间表现出弱铁磁耦合,而配合物4表现出镧系单离子磁性。配合物4的交流磁化率表明,同相(χ')和异相(χ'')信号均与频率和温度有关,这是U = 124.5 K时场诱导磁化缓慢弛豫的典型特征。配合物4在2 K时还表现出明显的蝶形磁滞回线,表明它是一种单离子磁体。此外,配合物4表现出较强的荧光发射,这是镧系离子典型的窄发射带。因此,配合物4可被视为一种分子磁性和发光材料。相比之下,配合物2表现出非常弱的基于Dy的发射,因为顺磁性Ni离子猝灭了荧光,从而降低了三重态的粒子数。