Unprecedented Selenium and Lanthanide Simultaneously Bridging Selenotungstate Aggregates Stabilized by Four Tetra-vacant Dawson-like {Se2W14} Units

Hai Lou Li, Ya Jie Liu, Ya Min Li, Li Juan Chen*, Jun Wei Zhao, Guo Yu Yang

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

17 Citations (Scopus)

Abstract

In the presence of the larger [H2N(CH3)2]+ and K+ counter cations as structure-stabilizing agents, a class of unprecedented selenium and lanthanide (Ln) simultaneously bridging tetra-vacant Dawson-like selenotungstate aggregates [H2N(CH3)2]2Na9K2H19{[Ln4W4 Se4O22(H2O)5](Se2W14O52)2}2⋅60 H2O [Ln=TbIII (1), DyIII (2), HoIII (3), ErIII (4), TmIII (5), YbIII (6)] have been obtained by the one-pot assembly reaction of Na2WO4⋅2 H2O, Ln(NO3)3⋅6 H2O, and Na2SeO3 under moderately acidic aqueous conditions and the complexes were structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. It should be noted that the appropriate molar ratio of Se/W is extremely important in the formation of 1–6 and can effectively ameliorate the yield of 1–6. Moreover, dimethylamine hydrochloride is also indispensable and plays a considerably important role in improving the solubility of Ln ions and stabilizing the structures of 1–6. The main polyoxoanion skeletons of 1–6 are constructed from two sandwich-type tetra-vacant Dawson-like {[Ln4W4Se4O22(H2O)5](Se2W14O52)2}16− half-units linked through two W-O-Ln bridges. The sandwich-type half-unit comprises two tetra-vacant Dawson-like [Se2W14O52]12− fragments encapsulating a unique dodecanuclear Se-Ln-W [Ln4W4Se4O22(H2O)5]8+ oxo cluster. Their solid-state visible and NIR fluorescent properties and lifetime decay behaviors were measured and their solid-state luminescent spectra mainly demonstrate the characteristic emission bands of Ln3+ ions. Moreover, the dominant wavelengths, the color purity, and correlated color temperatures of 1–5 have been also calculated. In addition, the luminous flux values of 1–5 are 2031, 6992, 3071, 921, and 477 lumen, respectively.

Original languageEnglish
Pages (from-to)2897-2907
Number of pages11
JournalChemistry - An Asian Journal
Volume13
Issue number19
DOIs
Publication statusPublished - 4 Oct 2018

Keywords

  • lanthanides
  • luminescent properties
  • polyoxometalates
  • selenotungstates
  • tetra-vacant Dawson structure

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