When in a 1:1 mole ratio, copper(I) cations assemble with a bis-bidentate ligand, L, in dichloromethane to form a [Cu4L4]4+ supramolecular square. Spectrophotometric titration data is modelled to reveal snapshots of the entire assembly and disassembly process, including detailed thermodynamic information on the step-wise reactions. NMR results corroborate the existence of 4 additional supramolecular assemblages other than the grid itself. The assembly is entropy driven as solvent molecules are released from the coordination sphere of the metal cations. The coulombic cost of bringing 4 monocations into close proximity appears to be about 30 kJ/mol in acetonitrile. The fidelity of the target structure will be discussed in detail. 

Self-assembly snapshots of a 2�2 copper(I) supramolecular grid

248th National Meeting (2014)

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