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Addition of 2 equiv. of CuI to a [Cu]4 multimetallic complex results in cluster formation leading to the isolation of a rare bicapped tetrahedral [Cu6I2] cluster that is stabilised by two conformationally constrained polynucleating ligands.

Graphical abstract: Isolation of an unusual [Cu6] nanocluster through sequential addition of copper(i) to a polynucleating ligand

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