Improvement of the Photophysical Performance of Platinum-Cyclometalated Complexes in Halogen-Bonded Adducts

Three groups of luminescent platinum complexes [Pt(C^N)(L)(Y)] [C^N=benzothienyl-pyridine (1), bezofuryl-pyridine (2), phenyl-pyridine (3); L/Y=DMSO/Cl (a), PPh₃ /Cl (b), PPh₃ /CN (c)] have been probed as halogen-bond (XB) acceptors towards iodofluorobenzenes (IC₆ F₅ and I₂ C₆ F₄ ). Compounds 1 a and 2 a (L/Y=DMSO/Cl) afford the adducts 1 a⋅⋅⋅I₂ C₆ F₄ and 2 a⋅⋅⋅I₂ C₆ F₄ , which feature I⋅⋅⋅S_btpy /I⋅⋅⋅π_btpy and I⋅⋅⋅O_DMSO /I⋅⋅⋅Cl short contacts, respectively. The phosphane-cyanide derivatives 1 c and 2 c (L/Y=PPh₃ /CN) co-crystallise with both IC₆ F₅ and I₂ C₆ F₄ . None of the phpy-based species 3 a-3 c participated in XB interactions. Although the native complexes are rather poor luminophores in the solid state (Φ_em =0.023-0.089), the adducts exhibit an up to 10-fold increase of the intensity with a minor alteration of the emission energy. The observed gain in the quantum efficiency is mainly attributed to the joint influence of non-covalent interactions (halogen/hydrogen bonding, π-π stacking), which govern the crystal-packing mode and diminish the radiationless pathways for the T₁ →S₀ transition by providing a rigid environment around the chromophore.