Sokolova Elina V, Kinzhalov Mikhail A, Smirnov Andrey S, Cheranyova Anna M, Ivanov Daniil M, Kukushkin Vadim Yu, Bokach Nadezhda A
Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, Russian Federation.
Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, Tomsk 634050, Russian Federation.
ACS Omega. 2022 Sep 13;7(38):34454-34462. doi: 10.1021/acsomega.2c04110. eCollection 2022 Sep 27.
Cyclometalated platinum(II) complexes [Pt(ppy)Cl(CNAr)] (ppy = 2-phenylpyridinato-C,; Ar = CH-2-I , CH-4-I , CH-2-F-4-I , and CH-2,4-I ) bearing ancillary isocyanide ligands were obtained by the bridge-splitting reaction between the dimer [Pt(ppy)(μ-Cl)] and 2 equiv any one of the corresponding CNAr. Complex was crystallized in two polymorphic forms, namely, and , exhibiting green (emission quantum yield of 0.5%) and orange (emission quantum yield of 12%) phosphorescence, respectively. Structure-directing non-covalent contacts in these polymorphs were verified by a combination of experimental (X-ray diffraction) and theoretical methods (NCIplot analysis, combined electron localization function (ELF), and Bader quantum theory of atoms in molecules (QTAIM analysis)). A noticeable difference in the spectrum of non-covalent interactions of and is seen in the Pt···Pt interactions in and absence of these metallophilic contacts in . The other solid luminophores, namely, , , , and ·CHCl, exhibit green luminescence; their structures include intermolecular C-I···Cl-Pt halogen bonds as the structure-directing interactions. Crystals of , , , , , and ·CHCl demonstrated a reversible mechanochromic color change achieved by mechanical grinding (green to orange) and solvent adsorption (orange to green).
通过二聚体[Pt(ppy)(μ-Cl)]与2当量的任何一种相应的CNAr之间的桥裂解反应，得到了带有辅助异腈配体的环金属化铂(II)配合物[Pt(ppy)Cl(CNAr)]（ppy = 2-苯基吡啶-C；Ar = CH₂-I、CH₄-I、CH₂-F-4-I和CH₂,4-I）。配合物以两种多晶型形式结晶，即 和 ，分别呈现绿色（发射量子产率为0.5%）和橙色（发射量子产率为12%）磷光。通过实验（X射线衍射）和理论方法（NCIplot分析、组合电子定位函数（ELF）和巴德分子中原子量子理论（QTAIM分析））相结合，验证了这些多晶型物中的结构导向非共价相互作用。 在 的非共价相互作用光谱中，在 中存在Pt···Pt相互作用，而在 中不存在这些亲金属接触，这一点有明显差异。其他固体发光体，即 、 、 和 ·CHCl，呈现绿色发光；它们的结构包括分子间C-I···Cl-Pt卤键作为结构导向相互作用。 、 、 、 、 和 ·CHCl的晶体通过机械研磨（绿色变为橙色）和溶剂吸附（橙色变为绿色）实现了可逆的机械变色。
