Through-bond communication between polymer-bound phosphinic acid ligands and trivalent metal ions probed with FTIR spectroscopy

Add time:08/11/2019    Source:sciencedirect.com

The binding of trivalent metal ions to immobilized ligands is analyzed to determine the principal type of interaction, the extent of ion exchange, and changes due to through-bond communication. FTIR spectroscopy is found to be a readily accessible means of determining through-bond communication and spectra provide support for a molecular level interpretation of the interaction. The affinity of the phosphinic acid ligand for Al(III), La(III), Lu(III), Fe(III), and In(III) is quantified with distribution coefficients from 0.01–6 M nitric acid solutions. High affinities are evident with In(III) > Fe(III) > Lu(III) > La(III) > Al(III). The affinities correlate with the softness parameter and thus the polarizability of the metal ion. The FTIR spectrum of the phosphinic acid has two incompletely separated bands at 1168/1126 cm−1 associated with the PO bond and two similar bands at 967/951 cm−1 due to the PO(H) bond. The bands at 1168/951 and 1126/967 cm−1 are assigned to different hydrogen bonded conformers within the metal-free polymer. Through-bond communication is evident as the extent of metal ion binding increases: the PO and PO bands at 1168 and 951 cm−1, respectively, collapse into a single band between 1040 and 1080 cm−1 representative of PO2(M) while hydrogen bonding among unexchanged P(O)OH ligands gives the bands at 1133 and 981 cm−1.

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