65. Emerson, E. W.; Cain, M. F.; Sanderson, M. D.; Knarr, C. B.; Glueck, D. S.; Ahern, J. C.; Patterson, H. E.; Rheingold, A. L. Inorg. Chim. Acta 2015, 427, 168-172. Synthesis, structure, and luminescence of the “octahedral” cluster Cu4I4(rac-IsMePCH2PMeIs)2 (Is = 2,4,6-(i-Pr)3C6H2).

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Abstract

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.


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