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A new method for assessing the topology of metallosupramolecular assemblies using pyrene-appended ligands is reported. Two potentially tetradentate ligands containing one (L(1)) and two (L(2)) terminal pyrene moieties were synthesised and their complexes with Cu(+) and Cd(2+) were characterised. Photophysical measurements demonstrate that in [Cu(2)(L(1))(2)](2+), [CdL(1)](2+) and [Cu(2)(L(2))(2)](2+) the emission spectra are dominated by monomeric emission but in the cadmium complex of L(2) (where the pyrene units are in close proximity) a quenching of the luminescence coupled with weak emission at 540 nm is indicative of excimer formation.

Probing solution behaviour of metallosupramolecular complexes using pyrene fluorescence