一种基于磷的隔室配体，(S)P[N(Me)N=CH-C6H3-2-O-3-OMe]3 (LH3)，可用于组装发光的异双金属线性{L2Zn2Ln}+ [Ln = Gd, Tb, Nd 和 Eu]配合物。

A phosphorus-based compartmental ligand, (S)P[N(Me)N=CH-C6H3-2-O-3-OMe]3 (LH3), enables the assembly of luminescent heterobimetallic linear {L2Zn2Ln}+ [Ln = Gd, Tb, Nd and Eu] complexes.

机构信息

Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India.

出版信息

Dalton Trans. 2013 Nov 21;42(43):15447-56. doi: 10.1039/c3dt51431e.

Abstract

The sequential reaction of a phosphorus-based trishydrazone ligand, LH3 with anhydrous ZnCl2 and LnCl3·6H2O in a 2 : 2 : 1 stoichiometric ratio in the presence of triethylamine as the base leads to the formation of monocationic trinuclear complexes [L2Zn2Ln]Cl {Ln = Gd (1), Tb (2), Nd (3), Eu (4) and L = [(S)P[N(Me)N=CH-C6H3-2-O-3-OMe]3}. All the three metal ions, in each of these compounds, are arranged in a linear fashion. The two terminal Zn(II) ions are encapsulated by three imino and three phenolate oxygen atoms while the lanthanide ion remains in the centre with an all-oxygen coordination environment. Detailed photophysical measurements reveal the complete absence of antenna sensitization in all the four complexes. However, a strong emission was found for 2 and 4 when excited directly at their f-f levels.

摘要

具有磷基三腙配体 LH3 的连续反应，在三乙胺作为碱存在下，与无水 ZnCl2 和 LnCl3·6H2O 以 2:2:1 的化学计量比反应，生成单核三核配合物[L2Zn2Ln]Cl{Ln=Gd(1)，Tb(2)，Nd(3)，Eu(4)和 L= [(S)P[N(Me)N=CH-C6H3-2-O-3-OMe]3}。在这些化合物中，所有三个金属离子都以线性方式排列。两个末端的 Zn(II)离子被三个亚氨基和三个苯氧原子包围，而镧系元素离子则留在中心，具有全氧配位环境。详细的光物理测量表明，所有四个配合物中完全不存在天线敏化。然而，当直接在其 f-f 能级上激发时，发现 2 和 4 具有很强的发射。