Keggin-type polyoxometalate 1 : 1 complexes of Pb(ii) and Bi(iii): Experimental, theoretical and luminescence studies

Anna A. Mukhacheva, Tatiana Asanova, Maxim R. Ryzhikov, Taisiya S. Sukhikh, Nikolay B. Kompankov, Vadim V. Yanshole, Alexey S. Berezin, Artem L. Gushchin, Pavel A. Abramov, Maxim N. Sokolov

Результат исследования: Научные публикации в периодических изданияхстатьярецензирование

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 оригиналаанглийский
Страницы (с-по)6913-6922
Число страниц10
ЖурналDalton Transactions
Том50
Номер выпуска20
DOI
СостояниеОпубликовано - 25 мая 2021

Предметные области OECD FOS+WOS

  • 1.04 ХИМИЧЕСКИЕ НАУКИ
  • 1.04.EC ХИМИЯ, НЕОРГАНИЧЕСКАЯ И ЯДЕРНАЯ

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