Self-Assembly of Tunable Heterometallic Ln-Ru Coordination Polymers with Near-Infrared Luminescence and
Lei Wang1, Zhigang Xie1, Song Dang2
1State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P.R. China), Fax: (+86) 431 85262775.
Abstract:
A series of heterometallic lanthanide (Ln)-Ru coordination polymers, denoted Gd-1, Yb-2, and Nd-3, were prepared by solvothermal reaction of a carboxylate derivative of [Ru(bpy)3 ]2+ (Rubpy, bpy=2,2'-bipyridine), oxalic acid, and Ln(OAc)3 by using the metalloligand strategy. Single-crystal X-ray diffraction indicated that the resulting isostructural heterometallic complexes have 1D butterfly-shaped Ln-Ru-based coordination chains but show slight differences in the coordination environments of the Ln centers. The introduced Ru(bpy) metalloligands could act as good light-harvesting antennas to effectively sensitize near-infrared (NIR) luminescence by energy transfer from the triplet metal-to ligand charge transfer state of Rubpy units to Ln (Yb or Nd) under the excitation in the visible-light region. Additionally, dopant-concentration-dependent behavior of the Ru-based emission and sensitized NIR emission was demonstrated in Gd-1. Finally, the magnetocaloric effect of Gd-1 was studied. The preparation of such heterometallic coordination polymers offers a versatile platform to investigate dimensionally controlled properties.
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