The (2,2′-bipyridine)PtI2 complex with 5,5′-modification of fluorous side chains: Orthogonal skeleton

Abstract Two polyfluorinated PtI 2 -containing complexes, [5,5′-bis(R f CH 2 OCH 2 )-2,2′-bpy]PtI 2 [R f  = CF 3 - ( 5,5′-3F-PtI 2 ), HCF 2 CF 2 - ( 5,5′-4F-PtI 2 )], have been successfully synthesized. Interestingly, these two fluorous Pt-diimine complexes show two different types of structural features. For example, one fluorinated derivative 5,5′-4F-PtI 2 along with 5,5′-3F-PtBr 2 , which has been reported before, bear similarity to the C2/c (bpy)MX 2 platform. This simple (bpy)MX 2 platform with C2/c symmetry consists of orthogonal synthons in maintaining the synthons as columns and belts to accompany the introduced fluorous interactions. In contrast, the other fluorinated derivative 5,5′-3F-PtI 2 has been found to be completely different in the solid state. Its pattern of π⋯π interactions is a repetition of three molecular planes with the direction of the columns normal to the molecular planes, and its C3,3′ H⋯I interactions are partially kept though extensively modified. The dimer-monomer units utilize π⋯π stacking along the c -direction and C H⋯I hydrogen bonds along approximately the b -direction. The less dispersive fluorous components fill in space between the layers of 5,5′-3F-PtI 2 molecules parallel to bc -planes, where weak C H⋯F interactions are then enabled. Additionally, the electrical properties of 5,5′-3F-PtI 2 and two polymorphic 5,5′-3F-PtBr 2 vs. temperature have been studied. It can be easily seen that the fluorous side chain plays an important role in influencing their molecular packing, which in turn determine their electrical properties.