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We describe the synthesis and characterization of [Cu(POP)( 1 )][PF6], [Cu(POP)( 2 )][PF6], [Cu(xantphos)( 1 )][PF6], and [Cu(xantphos)( 2 )][PF6] in which ligands 1 and 2 are 2-(pyridin-2-yl)quinoline and 2-(6-methylpyridin-2-yl)quinoline, respectively. With 2,2'-bipyridine (bpy) as a benchmark, we assess the impact of the extended π-system on structural and solid-state photophysical properties. The single crystal structures of [Cu(POP)( 2 )][PF6], [Cu(xantphos)( 1 )][PF6], and [Cu(xantphos)( 2 )][PF6] were determined and confirmed a distorted tetrahedral copper(I) coordination environment in each [Cu(P^P)(N^N)]+ cation. The xanthene unit in [Cu(xantphos)( 1 )][PF6] and [Cu(xantphos)( 2 )][PF6] hosts the quinoline unit of 1 , and the 6-methylpyridine group of 2 . 1H NMR spectroscopic data indicate that these different ligand orientations are also observed in acetone solution. In their crystal structures, the [Cu(POP)( 2 )]+, [Cu(xantphos)( 1 )]+, and [Cu(xantphos)( 2 )]+ cations exhibit different edge-to-face and face-to-face π-interactions, but in all cases, the copper(I) centre is effectively protected by a ligand sheath. In [Cu(POP)( 2 )][PF6], pairs of cations engage in an efficient face-to-face -stacking embrace, and we suggest that this may contribute to this compound having the highest photoluminescence quantum yield (PLQY = 21%) of the series. With reference to data from the Cambridge Structural Database, we compare packing effects and PLQY data for the complexes incorporating 2-(pyridin-2-yl)quinoline and 2-(6-methylpyridin-2-yl)quinoline, with those of the benchmark bpy-containing compounds. We also assess the effect that Cu⋯O distances in the {Cu(POP)} and {Cu(xantphos)} domains of [Cu(P^P)(N^N)][X] compounds have on solid-state PLQY values.
