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

[Image: see text] 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).