TY - JOUR
T1 - Phosphorescence at Low Temperature by External Heavy-Atom Effect in Zinc(II) Clusters
AU - Kobayashi, Fumiya
AU - Ohtani, Ryo
AU - Teraoka, Saki
AU - Yoshida, Masaki
AU - Kato, Masako
AU - Zhang, Yingjie
AU - Lindoy, Leonard F.
AU - Hayami, Shinya
AU - Nakamura, Masaaki
N1 - Funding Information:
This work was supported by a KAKENHI Grant-in-Aid for Scientific Research (A) JP17H01200 and also by a JSPS Grant-in-Aid for Young Scientists (B) JP18K14245 as well as a JSPS Grant-in-Aid for Scientific Research on Innovative Areas (Mixed Anion JP17H05485, and Soft Crystals JP17H06367). This work was partially supported by the Cooperative Research Program of the “Network Joint Research Centre for Materials and Devices”. The single crystal data for 1, 4, and 5 were collected on the MX1 beamline at the Australian Synchrotron, a part of ANSTO. The computations were performed using the Research Center for Computational Science, Okazaki, Japan.
Funding Information:
This work was supported by a KAKENHI Grant-in-Aid for Scientific Research (A) JP17H01200 and also by a JSPS Grant-in-Aid for Young Scientists (B) JP18K14245 as well as a JSPS Grant-in- Aid for Scientific Research on Innovative Areas (Mixed Anion JP17H05485, and Soft Crystals JP17H06367). This work was partially supported by the Cooperative Research Program of the “Network Joint Research Centre for Materials and Devices”. The single crystal data for 1, 4, and 5 were collected on the MX1 beamline at the Australian Synchrotron, a part of ANSTO. The computations were performed using the Research Center for Computational Science, Okazaki, Japan.
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/4/23
Y1 - 2019/4/23
N2 - Luminescent Zn II clusters [Zn 4 L 4 (μ 3 -OMe) 2 X 2 ] (X=SCN (1), Cl (2), Br (3)) and [Zn 7 L 6 (μ 3 -OMe) 2 (μ 3 -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.
AB - Luminescent Zn II clusters [Zn 4 L 4 (μ 3 -OMe) 2 X 2 ] (X=SCN (1), Cl (2), Br (3)) and [Zn 7 L 6 (μ 3 -OMe) 2 (μ 3 -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.
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U2 - 10.1002/chem.201900343
DO - 10.1002/chem.201900343
M3 - Article
C2 - 30860310
AN - SCOPUS:85062816698
SN - 0947-6539
VL - 25
SP - 5875
EP - 5879
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 23
ER -