Excited state processes of dinuclear Pt(II) complexes bridged by 8-hydroxyquinoline

Dinuclear d⁸ Pt(II) complexes, where two mononuclear square planar Pt(II) units are bridged in an "A-frame" geometry, possess photophysical properties characterised by either metal-to-ligand-(MLCT) or metal-metal-ligand-to-ligand charge transfer (MMLCT) transitions determined by the distance between the two Pt(II) centres. When using 8-hydroxyquinoline (8HQH) as the bridging ligand to construct novel dinuclear complexes with general formula [C^NPt(μ-8HQ)]₂, where C^N is either 2-phenylpyridine (1) or 7,8-benzoquinoline (2), triplet ligand-centered (³LC) photophysics results echoing that in a mononuclear model chromophore, [Pt(8HQ)₂] (3). The lengthened Pt-Pt distances of 3.255 Å (1) and 3.243 Å (2) results in a lowest energy absorption centred around 480 nm assigned as having mixed LC/MLCT character by TD-DFT, mirroring the visible absorption spectrum of 3. Additionally, 1 and 2 exhibit ³LC photoluminescence with limited quantum yields (0.008) from broad transitions centred near 680 nm. Photoexcitation of 1-3 leads to an initially prepared excited state that relaxes within 15 ps to a ³LC excited state centred on the 8HQ bridge, which then persists for several microseconds. All the experimental results correspond well with DFT electronic structure calculations.