3 years ago

Iodobismuthate(III) and Iodobismuthate(III)/iodocuprate(I) Complexes with Organic Ligands

Howard H. Patterson, Aaron D. Nicholas, Francis H. Barnes, Andrew W. Kelly, Robert D. Pike, Amelia M. Wheaton
Pyridine ligand complexes of [Bu₄N][BiI₄] were prepared using chelating ligands 2,2ʹ-bipyridyl (2,2ʹ-Bpy), 1,10-phenanthroline (Phen), and 4-nitro-1,10-phenanthroline (NO₂Phen), producing monomeric complexes [Bu₄N][(2,2ʹ-Bpy)BiI₄], [Bu₄N][(Phen)BiI₄], and [Bu₄N][(NO₂Phen)BiI₄], and bridging ligands 4,4ʹ-bipyridyl (4,4ʹ-Bpy), pyrazine (Pyz), and aminopyrazine (NH₂Pyz) resulting in formation of polymers [Bu₄N]n[(4,4ʹ-Bpy)BiI₄]n and [Bu₄N]2n[(RPyz)Bi₂I₈]n (R = H, NH₂). The latter contain edge-sharing Bi₂I₈ dimers. Organic ligand Bi(III)/Cu(I) clusters [Bu₄N]₂[L₂Bi₂Cu₂I₁₀] (L = PPh₃, P(OPh)₃) and [Bu₄N]₂[PyBi₂Cu₂I₁₀] (Py = pyridine) have been prepared. All bismuthate(III) centers are distorted octahedra and all cuprate(I) centers are tetrahedral, with organic ligands bonded to Cu(I). The first neutral BiI₃/CuI organic ligand complex [(PPh₃)₆BiCu₃I₆] is reported. Diffuse reflectance spectroscopy measurements reveal strong absorption bands for both iodobismuthate(III) and iodocuprate(I)/bismuthate(III) complexes in the UV and visible range. Despite the similarity in absorption bands, DFT calculations support a distinct shift in transition from a mixed halide/metal-to-ligand charge transfer (X/MLCT) to a metal-halide cluster-centered transition upon incorporation of copper(I) into the cluster.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejic.201701052

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