Synthesis, structure, and luminescence of the “octahedral” cluster Cu4I4(rac-IsMePCH2PMeIs)2 (Is = 2,4,6-(i-Pr)3C6H2)

• The cluster Cu4I4(rac-IsMePCH2PMeIs)2 (1, Is = 2,4,6-(i-Pr)3C6H2) was prepared.
• The crystal structure of 1·4CHCl3 showed a distorted “octahedral” geometry.
• Cluster 1 showed temperature-dependent emission from 3XLCT and 3CC excited states.

Reaction of the bis(phosphine) rac-IsMePCH2PMeIs (Is = 2,4,6-(i-Pr)3C6H2) with 2 equiv. of CuI gave the complex Cu4I4(rac-IsMePCH2PMeIs)2 (1) as a mixture of two diastereomers. The crystal structure of 1·4CHCl3 showed it adopted a distorted “octahedral” geometry with a rectangular Cu4 plane, two asymmetrically bridging μ4-iodides, two μ2-iodides and two bis(phosphines) bridging two copper atoms. On UV excitation in the solid state, cluster 1 showed temperature-dependent emission from 3XLCT (halide-to-ligand charge transfer) and 3CC (Cu4I4 cluster-centered) excited states.

Bulky P-substituents in a bridging bis(phosphine) supported an unusual “octahedral” cluster, which showed temperature-dependent emission from 3XLCT (halide-to-ligand charge transfer) and 3CC (Cu4I4 cluster-centered) excited states.Figure optionsDownload as PowerPoint slide