Craze Alexander R, Huang Xin-Da, Etchells Isaac, Zheng Li-Min, Bhadbhade Mohan M, Marjo Christopher E, Clegg Jack K, Moore Evan G, Avdeev Maxim, Lindoy Leonard F, Li Feng
School of Science and Health, University of Western Sydney, Penrith, NSW 2751, Australia.
State Key Laboratory of Coordination Chemistry, Institute of Coordination Chemistry at Nanjing University, Qixia District, Nanjing, Jiangsu Province, China.
Dalton Trans. 2017 Sep 28;46(36):12177-12184. doi: 10.1039/c7dt02556d. Epub 2017 Sep 5.
This paper presents the synthesis of a tripodal ligand (HL) via the Schiff base condensation of N,N-diethylsalicylaldehyde and tris(2-aminoethyl)amine. The neutral complexes of type [EuL], [GdL] and [DyL] were synthesized and characterized by FT-IR, SEM-EDS, PXRD, single crystal X-ray diffraction, CHN analysis and high resolution ESI-MS. X-ray crystallographic studies demonstrated that the heptadentate ligand incorporating a cavity pre-organized by hydrogen bonding binds the Ln(iii) ions to yield a face capped octahedral coordination geometry with three-fold symmetry. Photoluminescence studies show a typical Ln(iii) absorption character for the three complexes, with [EuL] demonstrating considerably stronger lanthanide-based luminescence peaks, and a Eu(iii) centered luminescence lifetime of 0.144 ± 0.01 ms. Temperature/field-dependent DC and temperature/frequency-dependent AC magnetic measurements carried out for the Dy(iii) complex indicated obvious magnetic anisotropy and suggested slow relaxation behaviour with considerable quantum tunnelling of the magnetization contribution.
本文介绍了通过N,N - 二乙基水杨醛与三(2 - 氨基乙基)胺的席夫碱缩合反应合成三脚架配体(HL)。合成了[EuL]、[GdL]和[DyL]型中性配合物,并通过傅里叶变换红外光谱(FT - IR)、扫描电子显微镜 - 能谱仪(SEM - EDS)、粉末X射线衍射(PXRD)、单晶X射线衍射、元素分析(CHN)和高分辨率电喷雾电离质谱(ESI - MS)对其进行了表征。X射线晶体学研究表明,通过氢键预组织形成一个空腔的七齿配体与Ln(iii)离子结合,形成具有三重对称性的面帽八面体配位几何结构。光致发光研究表明这三种配合物具有典型的Ln(iii)吸收特征,其中[EuL]表现出相当强的基于镧系元素的发光峰,且Eu(iii)中心发光寿命为0.144±0.01 ms。对Dy(iii)配合物进行的温度/磁场依赖的直流和温度/频率依赖的交流磁性测量表明存在明显的磁各向异性,并表明具有相当大的磁化贡献量子隧穿的慢弛豫行为。