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Kromer, Sarah; Roy, Subhangi; Yarnell, James E.; Taliaferro, Chelsea M.; Castellano, Felix N. (, Dalton Transactions)Dinuclear d 8 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 ( 3 LC) 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 3 LC 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 3 LC excited state centred on the 8HQ bridge, which then persists for several microseconds. All the experimental results correspond well with DFT electronic structure calculations.more » « less
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Kim, Tae Wu; Kim, Pyosang; Mills, Alexis W.; Chakraborty, Arnab; Kromer, Sarah; Valentine, Andrew J.; Castellano, Felix N.; Li, Xiaosong; Chen, Lin X. (, The Journal of Physical Chemistry C)