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Published on: August 2, 2012
Hierarchical subcomponent self-assembly of covalent triple-stranded complexes with 3d-4f vertices: luminescence and
Zhi Liu1,2, Fan Yin1,2, Jian Yang2
1College of Chemistry, Fuzhou University, Fuzhou 350108, People's Republic of China. tianchongbin@fjirsm.ac.cn.
Abstract:
Well-defined 3d-4f heterometallic supramolecular architectures have attracted attention because of their applications in the field of luminescence and magnetism. However, covalent metallo-supramolecular discrete complexes, decorated with hetero-metallic vertices, have never been reported because of the difficulties in design and control. Herein, we report a series of covalent metallo-supramolecular discrete complexes with 3d-4f vertices synthesized by hierarchical subcomponent self-assembly of tris(2-aminoethyl)amine, 2,6-diformyl-p-cresol, and lanthanide ions (Ln) with different amines and transition metal ions. The programmable self-assembly process results in the formation of triple-stranded hetero-metallic covalent organic discrete complexes, namely 3a-3c-(Ln, Zn) (Ln = SmIII, EuIII, DyIII, YbIII and LuIII) and 3a'-(Dy, Co), which are characterized by nuclear magnetic resonance (NMR) analysis, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and single-crystal X-ray analysis. Photophysical investigations disclose that the organic skeleton of 3a-(Ln, Zn) exhibits an excellent sensitizing ability toward SmIII, EuIII, and YbIII ions, displaying characteristic luminescence emission in both the visible and near-infrared (NIR) regions. AC susceptibility measurements of 3a'-(Dy, Co) reveal the frequency-independent performance under zero dc field, suggesting the absence of slow relaxation of magnetization. This work offers a new approach for the fabrication of discrete metallic covalent architectures with 3d-4f vertices.
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