Structure control and crystal-to-crystal transformation for two series of lanthanide–organic coordination polymers

Abstract

Two series of lanthanide-based coordination polymers, [Ln(HCPOB)(CPOB)(H₂O)₂]_n [Ln = Eu(a1), Gd(a2), Tb(a3), Dy(a4), Ho(a5), Er(a6)] and [Ln(HCPOB)(CPOB)]_n [Ln = Eu(b1), Gd(b2), Tb(b3), Dy(b4), Ho(b5), Er(b6)], have been synthesized using an asymmetric semi-rigid V-shape multicarboxylate ligand [H₄CPOB = 2-(4-carboxyphenoxy)benzoic acid] by a hydrothermal method at different temperatures. Series a were obtained at 130 °C and have one-dimensional (1D) chain architectures, while series b were synthesized at 180 °C and exhibit three-dimensional (3D) structures. Interestingly, temperature-dependent XRD patterns for 1D compounds indicate that the 1D structure changes to form the 3D coordination polymers on heating the crystals. Single crystals of series a can transform into crystals of series b without any significant change in crystal quality. The variations from 1D to 3D coordination structures are attributed to variable coordination modes of multicarboxylate ligand H₂CPOB. In addition, we have studied the luminescent properties of Eu³⁺, Tb³⁺, and Dy³⁺ compounds of series a and series b, and found that series a give very weak luminescence because of coordinated water molecules existing in the complexes. Due to the “antenna effect” or “luminescence sensitization”, series b exhibit much stronger fluorescent intensity than that of series a.