Synthesis, crystal structure, photoluminescence property of a series of 3d–4f coordination supramolecular complexes

• A series of 3d–4f heterobinuclear complexes have been synthesized.
• The photoluminescence (PL) spectra of complexes have been studied in detail.
• Different 3d metal ions could affect on the PL properties of LnIII ions.

A series of 3d–4f heterobinuclear complexes were constructed by employing the 2,2′-bipy (2,2′-bipy = 2,2′-bipyridine) ligand and corresponding metal ions (MII/LnIII, M = CoII, CuII and ZnII; LnIII = NdIII, SmIII, EuIII and TbIII). Elemental analyses, IR, UV–vis–NIR spectra, PXRD and single crystal X-ray diffraction analysis reveal that complexes 1–4, 5–8, and 9–12 are isomorphous, respectively. The zero-dimensional structures are further connected to 2D or 3D supramolecular network structures via extensive intermolecular hydrogen bonds. Luminescence studies for the heterobinuclear complexes containing SmIII, EuIII and TbIII reveal that the chromophoric composed of ZnII/L may efficiently sensitize the luminescence of the rare earth cations which acts as an antenna, whereas the existence of CuII leads to the quenching of the luminescence of LnIII ions.

A series of 3d–4f heterobinuclear complexes: [Co(2,2′-bipy)3][Ln(NO3)6]·H3O (1–4), [Cu(2,2′-bipy)2Ln(NO3)5(CH3OH)] (5–8) and [Zn(2,2′-bipy)2][Ln(NO3)6]·H3O (9–12) (2,2′-bipy = 2,2′-bipyridine; Ln = Nd, Sm, Eu and Tb) have been synthesized under hydrothermal conditions. X-ray single crystal study shows that complexes 1–2 and 5–6 are both crystallizing in triclinic, space group P-1. The influence of the d-block transition metal ions on the luminescence properties of Ln3+ ions in the solid state for these complexes has been studied in detail.Figure optionsDownload as PowerPoint slide