Hidden Heterometallic Interaction Emerging from Resonant Inelastic X-ray Scattering in Luminescent Tb-Pt Molecules
Hidden Heterometallic Interaction Emerging from Resonant Inelastic X-ray Scattering in Luminescent Tb-Pt Molecules
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发光 Tb-Pt 分子中共振非弹性 X 射线散射产生的隐藏异金属相互作用
DOI：
10.1021/acs.jpcc.2c01396
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发表时间：
2022
影响因子：
3.7
通讯作者：
and Masahiro Yama
中科院分区：
文献类型：
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作者：
Takefumi Yoshida;Ahmed Shabana;David Chukwuma Izuogu;Kentaro Fuku;Tetsu Sato;Haitao Zhang;Yukina Yamamoto;Jun Kamata;Hitomi Ohmagari;Miki Hasegawa;Goulven Cosquer;Shinya Takaishi;Takuma Kaneko;Tomoya Uruga;Yasuhiro Iwasawa;and Masahiro Yama
理论计算通常用于检查金属间相互作用。然而，为了验证该理论，需要实验证实这些相互作用的存在。我们合成了新的稀土金属配合物NEt 4 {[Pt（PhSAc）4]Ln[（PhSAc）4Pt]}·2DMF（Ln：镧系元素= Gd（1），Tb（2），Dy（3），PhSAc =苯并硫代乙酸盐，NEt 4 =四乙基铵），其中两个反磁性的Pt（II）离子与中心的Ln（III）离子相互作用。通常，这些相互作用不会被检测到，因为Ln和Pt原子之间的距离（1.36 nm）远大于共价半径（1.33 nm）和离子半径（1.30 nm）。Pt-LIII共振非弹性X射线散射（RIXS）分析进行了实验确认的独特影响的隐藏的Ln-Pt相互作用的发光的Tb-Pt分子，其中的相互作用诱导的发射性质的Tb和Pt离子，具有高的量子产率（59%）。分子中原子的量子理论（QTAIM）分析也被用来证实实验结果。RIXS分析允许识别的协调环境，包括异金属相互作用的存在下，影响所观察到的发光的几个独特的特征。
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–LIIIresonant 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.