Polymorph-Dependent Phosphorescence of Cyclometalated Platinum(II) Complexes and Its Relation to Non-covalent Interactions.

Autor: Sokolova EV; Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, Russian Federation., Kinzhalov MA; 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., Smirnov AS; Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, Russian Federation., Cheranyova AM; Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, Russian Federation., Ivanov DM; 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., Kukushkin VY; Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, Russian Federation.; Institute of Chemistry and Pharmaceutical Technologies, Altai State University, Barnaul 656049, Russian Federation., Bokach NA; 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.
Jazyk: angličtina
Zdroj: ACS omega [ACS Omega] 2022 Sep 13; Vol. 7 (38), pp. 34454-34462. Date of Electronic Publication: 2022 Sep 13 (Print Publication: 2022).
DOI: 10.1021/acsomega.2c04110
Abstrakt: Cyclometalated platinum(II) complexes [Pt(ppy)Cl(CNAr)] (ppy = 2-phenylpyridinato-C 2 , N ; Ar = C 6 H 4 -2-I 1 , C 6 H 4 -4-I 2 , C 6 H 3 -2-F-4-I 3 , and C 6 H 3 -2,4-I 2 4 ) bearing ancillary isocyanide ligands were obtained by the bridge-splitting reaction between the dimer [Pt(ppy)(μ-Cl)] 2 and 2 equiv any one of the corresponding CNAr. Complex 2 was crystallized in two polymorphic forms, namely, 2 I and 2 II , 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 2 I and 2 II is seen in the Pt···Pt interactions in 2 II and absence of these metallophilic contacts in 2 I . The other solid luminophores, namely, 1 , 3 I-II , 4 , and 4 ·CHCl 3 , exhibit green luminescence; their structures include intermolecular C-I···Cl-Pt halogen bonds as the structure-directing interactions. Crystals of 1 , 2 I , 3 I , 3 II , 4 , and 4 ·CHCl 3 demonstrated a reversible mechanochromic color change achieved by mechanical grinding (green to orange) and solvent adsorption (orange to green).
Competing Interests: The authors declare no competing financial interest.
(© 2022 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
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