Polymorphism and Mechanochromism in 2-Phenylbenzothiazole Cyclometalated Pt(II) Complexes with Chelating N(∧)O Ligands

[Image: see text] New cyclometalated Pt(II) complexes with 2-phenylbenzothiazole (pbt) and two different picolinate ligands [Pt(pbt)(R-pic-κN,O)] (R = H (1), OH (2)) were prepared. In contrast to 1, the OH substituent group on 2 allows modulation of the packing in the solid state through donor–acceptor H-bonding interactions with the CH(2)Cl(2) solvent. Thus, three pseudopolymorphs of 2 with different aggregation degrees were isolated, including yellow 2-Y, orange-red 2-R (2·0.5CH(2)Cl(2)) and black 2-B (2·0.75CH(2)Cl(2)) with emissions at 540, 656, and 740 nm, respectively, in the solid state at 298 K. 2-R and 2-B can be transformed to the pristine solid 2. Studies of their crystal structures show that 1 and 2-Y stack in columns with only π···π stacking interactions, whereas 2-R displays strong aggregated 1D infinite chains based on Pt···Pt and π···π stacking interactions, consistent with the colors and the photophysical properties, measured in several media. Interestingly, 1 and 2 exhibit reversible mechanochromic behavior with high contrast in the color and color emission upon mechanical grinding due to a phase transition between a crystalline and an amorphous state, as confirmed by powder X-ray diffraction (PXRD) studies. Theoretical calculations indicate that Pt···Pt contacts are more relevant in the trimers and tetramers than in the dimers, particularly in their T(1) states, associated with a change from a (3)IL/(3)MLCT transition in the monomer to (3)MM(L+L′)CT in the oligomers. Noncovalent interaction (NCI) theoretical studies indicate that the π···π stacking among chelates also exerts a strong influence in the metal-metal-to-ligand charge transfer transition character.