Phosphorescence at Low Temperature by External Heavy-Atom Effect in Zinc(II) Clusters

Fumiya Kobayashi, Ryo Ohtani, Saki Teraoka, Masaki Yoshida, Masako Kato, Yingjie Zhang, Leonard F. Lindoy, Shinya Hayami, Masaaki Nakamura

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Abstract

Luminescent Zn II clusters [Zn 4 L 43 -OMe) 2 X 2 ] (X=SCN (1), Cl (2), Br (3)) and [Zn 7 L 63 -OMe) 23 -OH) 4 ]Y 2 (Y=I (4), ClO 4 (5)), HL=methyl-3-methoxysalicylate, exhibiting blue fluorescence at room temperature (λ max =416≈429 nm, Φ em =0.09–0.36) have been synthesised and investigated in detail. In one case the external heavy-atom effect (EHE) arising the presence of iodide counter anions yielded phosphorescence with a long emission lifetime (λ max =520 nm, τ=95.3 ms) at 77 K. Single-crystal X-ray structural analysis and time-dependent density-functional theory (TD-DFT) calculations revealed that their emission origin was attributed to the fluorescence from the singlet ligand-centred ( 1 LC) excited state, and the phosphorescence observed in 4 was caused by the EHE of counter anions having strong CH−I interactions.

Original languageEnglish
Pages (from-to)5875-5879
Number of pages5
JournalChemistry - A European Journal
Volume25
Issue number23
DOIs
Publication statusPublished - Apr 23 2019

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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    Kobayashi, F., Ohtani, R., Teraoka, S., Yoshida, M., Kato, M., Zhang, Y., Lindoy, L. F., Hayami, S., & Nakamura, M. (2019). Phosphorescence at Low Temperature by External Heavy-Atom Effect in Zinc(II) Clusters. Chemistry - A European Journal, 25(23), 5875-5879. https://doi.org/10.1002/chem.201900343