摘要： Two lanthanide-based metal–organic frameworks, [Tb2(5-nip)3(H2O)5·5H2O]n (1), and [Eu3(5-nip)4(5-Hnip)(H2O)7·9H2O]n (2) (5-H2nip = 5-nitroisophthalic acid), have been synthesized and structurally characterized. 1 features a unique 3D network with two distinct paddlewheel building blocks. 2 displays a 3D supramolecular framework with 1D channels occupied by free water molecules. Solid-state photoluminescence studies indicate that both the compounds 1 and 2 exhibit characteristic luminescence emission bands of the corresponding lanthanide ions in the visible region at room temperature. TG-DSC curves show that the dehydrated products of the title compounds exhibit high stability up to 400 °C. The enthalpy changes of liquid-phase reaction of formation for 1 and 2, (l), were determined at 298.15 K by a microcalorimeter to be (10.7 ± 0.1) kJ·mol-1 and (30.6 ± 0.1) kJ·mol-1, respectively. Based on a designed thermochemical cycle, that of solid-phase reaction of formation and the standard molar enthalpy of formation for 1, (s) and , were calculated to be (16.9 ± 0.6) kJ·mol-1 and -(3103.2 ± 15.3) kJ·mol-1, respectively. Those for 2 were (119.4 ± 0.8) kJ?mol-1 and -(4510.2 ± 17.4) kJ?mol-1, respectively. Combining the thermochemical data of the reactions and kinetic equations with the data of thermokinetic experiments, the fundamental thermodynamic and kinetic parameters were also achieved.