Eu3+-Mediated Polymerization of Benzenetetracarboxylic Acid Studied by Spectroscopy, Temperature-Dependent Calorimetry, and Density Functional Theory

Thermodynamic parameters for the complexation of Eu3+ with pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid, BTC) as a model system for polymerizable metal-complexing humic acids were determined using temperature-dependent time-resolved laser-induced fluorescence spectroscopy (TRLFS) and isothermal titration calorimetry (ITC). At low metal and ligand concentrations (<50 mu M Eu3+, <1 mM BTC), a 1:1 monomeric Eu-BTC complex was identified in the range of 25-60 degrees C. At elevated concentrations (>500 mu M Eu3+ and BTC) a temperature-dependent polymerization was observed, where BTC monomers are linked via coordinating shared Eu3+ ions. The two methods lead to comparable thermodynamic data (Delta H=13.5 +/- 1.5/16.5 0.1 kJ mol(-1); Delta S = 152 +/- 5/130 SJ mol(-1) K-1; TRLFS/ITC) in the absence of polymerization. With the onset, of polymerization, TRLFS reveals the water coordination number of the lanthanide, whereas calorimetry is superior in determining the thermodynamic data in this regime. Evaluating the heat uptake kinetics, the monomer and polymer formation steps could be separated by "time-resolved" ITC, revealing almost identical binding enthalpies for the sequential reactions. Structural features of the complexes were studied by Fourier-transform infrared (FTIR) spectroscopy in combination with density functional theory (DFT) calculations showing predominantly chelating coordination with two carboxylate groups in the monomeric complex and monodentate binding of a single carboxylate group in the polymeric complex of the polycarboxylate with Eu3+. The data show that pyromellitic acid is a suitable model for the study of metal-mediated polymerization as a crucial factor in determining the effect of humic acids on the mobility of heavy metals in the environment.