Copper(I) Complexes of Bipyridine and Terpyridine with Fluorous Tails and the Formation of Crystalline Materials with Fluorous Layers

Copper(I) complexes with perfluorinated tails, (Cu I L 2 AcN)BF 4 and (Cu I L 3 AcN)BF 4 , where L 2 = 6,6″‐bis(perfluorohexyl)‐2,2′:6′,2″‐terpyridine and L 3 = 6,6′‐bis(2,2,3,3,4,4,5,5,6,6,7,7,7‐tridecafluoroheptyl)‐2,2′‐bipyridine and AcN = acetonitrile, were synthesized and their rather unique crystal structures were elucidated. (Cu I L 2 AcN)BF 4 crystallizes in a low‐symmetry space group, P $\bar {1}$ , with a very large unit cell that required synchrotron radiation to locate all atoms. The molecular structure of (Cu I L 2 AcN)BF 4 has an asymmetric tetrahedrally distorted square‐planar coordination sphere around Cu I . Eight similar but distinct molecular structures were found. The crystal packing of (Cu I L 2 AcN)(BF 4 ) has a layered structure with a clear segregation between the terpyridine moieties and the fluorous chains. The terpyridine units are arranged in a “back to back” fashion and tilted 20–25º relative to the interlayer plane, and the layered structure is staggered with offsets of approximately 4 Å between layers. The molecular structure of (Cu I L 3 AcN)(BF 4 ) features a Y‐shaped trigonal planar coordination sphere around copper(I). Comparison of the structure with analogous Cu I (neocuproine)AcN showed that the fluorous tails with the CH 2 CH 2 spacers basically have no effect on the bond lengths and angles to Cu 1 . The crystal structure of (Cu I L 3 AcN)(BF 4 ) shows a “herring bone” conformation with an approximately 96º angle in the CubipyAcN units. The “herring bone” conformation leads to an accordion‐type fluorous layer.