Lanthanide-Aromatic Iminodiacetate Frameworks with Helical Tubes: Structure, Properties, and Low-Temperature Heat Capacity.

ABSTRACT

A series of lanthanide coordination polymers [LnL(H2O)2] n [Ln = Pr (1), Nd (2), Sm (3), Eu (4), and Gd (5), H3L = N-(4-carboxy-benzyl)iminodiacetic acid] was hydrothermally prepared and structurally characterized. All the five compounds have been confirmed as 3D Ln-CPs with one-dimensional helical tunnels composed of four helical chains, although there are different coordination geometries around Ln3+. Enantiomeric helixes in 1-3, and absolute left-handed and right-handed helical chains in 4 and 5, respectively, lead to different tunnel spaces. Their conformations can also be featured by different space groups and unit cell dimensions. Photoluminescence measurement on 3 and 4 show characteristic emission peaks of Sm3+ and Eu3+ ions, respectively. The low-temperature heat capacity of 1-4 has been investigated in the temperature range of 1.9-300 K. Their heat capacity values are nearly equal below 10 K and display a crossover with the value order C p,m(2) > C p,m(1) ≈ C p,m(4) > C p,m(3) above 10 K. The measured heat capacities have been fitted, and the corresponding thermodynamic functions were consequently calculated based on the fitting parameters. The standard molar entropies at 298.15 K have been determined to be (415.71 ± 4.16), (451.32 ± 4.51), (308.53 ± 3.09), and (407.62 ± 4.08) J·mol-1·K-1 for 1, 2, 3, and 4, respectively.