A double rollover cycloplatinated(II) skeleton: a versatile platform for tuning emission by chelating and non-chelating ancillary ligand systems

摘要

Described here is the synthesis and characterization of heteroleptic binuclear platinum(ii) complexes of the type [Pt-2(-bpy-2H)(S<^>S)(2)] and [Pt-2(-bpy-2H)(L)(2)(X)(2)], containing a 2,2-bipyridine-based double rollover cycloplatinated core (Pt(-bpy-2H)Pt), in combination with the anionic S<^>S- chelate ligands di(ethyl)dithiocarbamate (dedtc) and O,O-di(cyclohexyl)dithiophosphate (dcdtp) or non-chelating L/X ancillary ligands (PPh3/Me, t-BuNC/Me, PPh3/SCN and PPh3/N-3). The new complexes were characterized using multinuclear (H-1, P-31 and Pt-195) NMR spectroscopy and some of them additionally using single crystal X-ray diffraction. The absorption and photoluminescence of the complexes show a strong dependence on the ancillary ligands. Upon excitation at 365 nm, in a CH2Cl2 rigid matrix (77 K), the complexes exhibit structured emission bands with (max) between 488 nm and 525 nm and vibrational spacing around 1350 cm(-1), indicating the excited states centered on the cyclometalated ligand ((ILCT)-I-3) with some mixing (MLCT)-M-3 characteristics. In the case of the PPh3/N-3 complex, a dual emission band (orange color) is observed in the solid state at 298 K for which the low energy band arises from an aggregation-induced emission (AIE). Upon lowering the temperature (77 K), thermochromism is observed (orange to yellow) which is accompanied by the intensification of the high energy band (ligand-centered structured band). Finally, in order to rationalize the obtained photophysical data, complete DFT (density functional theory) and TD-DFT (time-dependent DFT) calculations were performed on the selected complexes.