Аннотация
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 31P and 183W NMR spectroscopy, high-resolution electrospray mass-spectrometry (HR-ESI-MS) and cyclic voltammetry (CV). EXAFS and XANES data confirm the unchanged oxidation state and ψ-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 183W 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)4N)4K3[H4(PW11O39)2Bi]·25H2O (3) do not show sensitivity to water vapor.
Язык оригинала | английский |
---|---|
Страницы (с-по) | 6913-6922 |
Число страниц | 10 |
Журнал | Dalton Transactions |
Том | 50 |
Номер выпуска | 20 |
DOI | |
Состояние | Опубликовано - 25 мая 2021 |
Предметные области OECD FOS+WOS
- 1.04 ХИМИЧЕСКИЕ НАУКИ
- 1.04.EC ХИМИЯ, НЕОРГАНИЧЕСКАЯ И ЯДЕРНАЯ