TY - JOUR

T1 - Polymorph-Dependent Phosphorescence of Cyclometalated Platinum(II) Complexes and Its Relation to Non-covalent Interactions

AU - Sokolova, Elina V.

AU - Kinzhalov, Mikhail A.

AU - Smirnov, Andrey S.

AU - Cheranyova, Anna M.

AU - Ivanov, Daniil M.

AU - Kukushkin, Vadim Yu.

AU - Bokach, Nadezhda A.

N1 - Publisher Copyright: © 2022 The Authors. Published by American Chemical Society.

PY - 2022/9/27

Y1 - 2022/9/27

N2 - Cyclometalated platinum(II) complexes [Pt(ppy)Cl(CNAr)] (ppy = 2-phenylpyridinato-C2,N; Ar = C6H4-2-I 1, C6H4-4-I 2, C6H3-2-F-4-I 3, and C6H3-2,4-I2 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, 2I and 2II, 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 2I and 2II is seen in the Pt···Pt interactions in 2II and absence of these metallophilic contacts in 2I. The other solid luminophores, namely, 1, 3I-II, 4, and 4·CHCl3, exhibit green luminescence; their structures include intermolecular C-I···Cl-Pt halogen bonds as the structure-directing interactions. Crystals of 1, 2I, 3I, 3II, 4, and 4·CHCl3 demonstrated a reversible mechanochromic color change achieved by mechanical grinding (green to orange) and solvent adsorption (orange to green).

AB - Cyclometalated platinum(II) complexes [Pt(ppy)Cl(CNAr)] (ppy = 2-phenylpyridinato-C2,N; Ar = C6H4-2-I 1, C6H4-4-I 2, C6H3-2-F-4-I 3, and C6H3-2,4-I2 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, 2I and 2II, 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 2I and 2II is seen in the Pt···Pt interactions in 2II and absence of these metallophilic contacts in 2I. The other solid luminophores, namely, 1, 3I-II, 4, and 4·CHCl3, exhibit green luminescence; their structures include intermolecular C-I···Cl-Pt halogen bonds as the structure-directing interactions. Crystals of 1, 2I, 3I, 3II, 4, and 4·CHCl3 demonstrated a reversible mechanochromic color change achieved by mechanical grinding (green to orange) and solvent adsorption (orange to green).

UR - http://www.scopus.com/inward/record.url?scp=85138785540&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/2900223d-0b18-325a-aefc-8d0af4d6d8d0/

U2 - 10.1021/acsomega.2c04110

DO - 10.1021/acsomega.2c04110

M3 - Article

C2 - 36188282

VL - 7

SP - 34454

EP - 34462

JO - ACS Omega

JF - ACS Omega

SN - 2470-1343

IS - 38

ER -