Keggin-type polyoxometalate 1: 1 complexes of Pb(II) and Bi(III): experimental, theoretical and luminescence studies

摘要

Bi3+ and Pb2+ uptake by a monolacunary Keggin-type [PW11O39](7-) anion leads to the formation of [PW11O39Bi](4-) and [PW11O39Pb](5-) complexes with a stereochemically active lone pair at the incorporated heterometal. The two complexes were isolated as (TBA)(4)[PW11O39Bi] (1) and (TBA)(5)[PW11O39Pb] (2) and characterized by P-31 and W-183 NMR spectroscopy, high-resolution electrospray mass-spectrometry (HR-ESI-MS) and cyclic voltammetry (CV). EXAFS and XANES data confirm the unchanged oxidation state and psi-square pyramidal geometry of Bi3+ and Pb2+ in 1 and 2. DFT calculations were used in order to (i) confirm the absence of ligands attached to the heterometal sites in both complexes and localize the lone pair, and (ii) assign all signals in the W-183 NMR spectra. Complexes 1 and 2 demonstrate photoluminescence (PL). A reversible change in the PL spectra of both complexes in the presence of water vapor has been detected. On the contrary, PL data for sandwich-type ((CH3)(4)N)(4)K-3[H-4(PW11O39)(2)Bi]center dot 25H(2)O (3) do not show sensitivity to water vapor.