TY - JOUR
T1 - Hidden Heterometallic Interaction Emerging from Resonant Inelastic X-ray Scattering in Luminescent Tb-Pt Molecules
AU - Yoshida, Takefumi
AU - Shabana, Ahmed
AU - Izuogu, David Chukwuma
AU - Fuku, Kentaro
AU - Sato, Tetsu
AU - Zhang, Haitao
AU - Yamamoto, Yukina
AU - Kamata, Jun
AU - Ohmagari, Hitomi
AU - Hasegawa, Miki
AU - Cosquer, Goulven
AU - Takaishi, Shinya
AU - Kaneko, Takuma
AU - Uruga, Tomoya
AU - Iwasawa, Yasuhiro
AU - Yamashita, Masahiro
N1 - Funding Information:
This research was supported by JSPS KAKENHI Grant Numbers JP19H05631 (M.Y.), JP20K15293 (T.Y.), 20K15041 (H.O.), and 17H06374 (M.H.). Prof. M.Y. acknowledges the support of 111 projects (B18030) from China. HERFD-XANES and RIXS measurements were performed at the BL36XU beamline at SPring-8. Part of the work was supported by the New Energy and Industrial Technology Development Organization (NEDO). The authors would like to thank Editage ( www.editage.com ) for English language editing.
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022
Y1 - 2022
N2 - Theoretical calculations are typically utilized for examining intermetallic interactions. However, to validate the theory, experimental confirmation of the existence of these interactions is necessary. We synthesized new heterometallic Ln-Pt complexes, NEt4{[Pt(PhSAc)4]Ln[(PhSAc)4Pt]}·2DMF (Ln: lanthanoid = Gd (1), Tb (2), Dy (3), PhSAc = benzothioacetate, NEt4 = tetraethylammonium), in which both diamagnetic Pt(II) ions interact with the central Ln(III) ion. Typically, these interactions are not detected because the distance between Ln and Pt atoms (∼3.6 Å) is much larger than the covalent radius (∼3.3 Å) and ionic radius (∼3.10 Å). Pt-LIII resonant inelastic X-ray scattering (RIXS) analysis was conducted to experimentally confirm the unique influence of the hidden Ln-Pt interaction on the luminescence of the Tb-Pt molecule, where the interaction induced emission properties in the Tb and Pt ions, with high quantum yield (59%). Quantum theory of atoms in molecules (QTAIM) analysis was also used to confirm the experimental results. RIXS analysis allowed the identification of several distinctive characteristics of the coordination environment, including the existence of heterometallic interactions, that affected the observed luminescence.
AB - Theoretical calculations are typically utilized for examining intermetallic interactions. However, to validate the theory, experimental confirmation of the existence of these interactions is necessary. We synthesized new heterometallic Ln-Pt complexes, NEt4{[Pt(PhSAc)4]Ln[(PhSAc)4Pt]}·2DMF (Ln: lanthanoid = Gd (1), Tb (2), Dy (3), PhSAc = benzothioacetate, NEt4 = tetraethylammonium), in which both diamagnetic Pt(II) ions interact with the central Ln(III) ion. Typically, these interactions are not detected because the distance between Ln and Pt atoms (∼3.6 Å) is much larger than the covalent radius (∼3.3 Å) and ionic radius (∼3.10 Å). Pt-LIII resonant inelastic X-ray scattering (RIXS) analysis was conducted to experimentally confirm the unique influence of the hidden Ln-Pt interaction on the luminescence of the Tb-Pt molecule, where the interaction induced emission properties in the Tb and Pt ions, with high quantum yield (59%). Quantum theory of atoms in molecules (QTAIM) analysis was also used to confirm the experimental results. RIXS analysis allowed the identification of several distinctive characteristics of the coordination environment, including the existence of heterometallic interactions, that affected the observed luminescence.
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U2 - 10.1021/acs.jpcc.2c01396
DO - 10.1021/acs.jpcc.2c01396
M3 - Article
AN - SCOPUS:85129942726
SN - 1932-7447
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
ER -