Solvent Influence in Obtaining Diverse Coordination Symmetries of Dy(III) Metal Centers in Coordination Polymers: Synthesis, Characterization and Luminescent Properties

Six new Dy(III)-containing coordination polymers (CPs) have been synthesized emphasizing the role of solvent molecules in directing the formation of the Dy(III) coordination sphere which in turn influences the dimensionality of the coordination polymer, thermal stability, and emission properties. An isophthalate-based flexible ligand 5-[(anthracen-9-ylmethyl)-amino]-isophthalic acid (H2L) with different solvents such as dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), diethylformamide (DEF), and N-donor linkers phen (1,10-phenanothroline) and pyridine (py) was employed to obtain six different coordination polymers, viz., [Dy-2(L)(2) (HCOO)(3) (DMF)center dot Me2NH2 center dot H2O](n) (1) , [Dy-4(L)(6) (DMA)(2) (H2O)(4)center dot 4DMA center dot 4H(2)O](n), (2), [Dy-2(L)(3)(DMSO)(3)(H2O)(2) center dot 2DMSO center dot 2H(2)O](n), (3), [{Dy(L)(DEF)}(2)(mu(2) -OH)](n) (4), [Dy-2(L)(3)(phen)(2) center dot DMA center dot 7H(2)O](n) (5), and [Dy(L)(NO3)(py)(2)center dot py](n) (6), respectively. All the compounds were characterized by IR spectroscopy and thermogravimetric analysis, and unambiguously characterized by single crystal X-ray crystallography. The bulky anthracenyl group of the linker H2L in combination with the solvent molecules significantly alters the coordination symmetry of the Dy(III) coordination sphere in the polymers in the manner: D-24 in 1, C-2v and D-4d in 2, C-4v , and C in 3, C-5v in 4, D-4d in 5, and D-2d in 6. The coordination symmetry plays an interesting role in sensitization of lanthanide emission. The emission maxima of compounds 1-6 vary from the blue region to the yellow region significantly due to coordination symmetry expressed by the Dy(III) centers, which in turn depends upon the coordinated solvent molecule. The thermogravimetric profile indicates the thermal stability of the solvent free compounds up to 300 degrees C.