Complexes with transition metals were assembled by reflux in MeOH solution of 1Gal with NiCl2 or Zn(OAc)2, in a 2:1 molar ratio. Complexes formed readily and could be isolated by simple evaporation of the solvent or centrifugation followed by drying, with no evidence of unreacted ligand. All complexes had distinct 1 H NMR spectra featuring characteristic broadening of peaks, particularly those corresponding to the dpa motif and anomeric protons. IR spectra showed slight shifts in characteristic peaks corresponding to the amide C=O stretch, and the fingerprint region to varying degrees (Figure S-20, ESI †). UV-Vis spectra for both complexes, Figure , show a structured absorbance feature with λmax = 274 nm, with stronger absorbance than the ligand at the same concentration, and a band at λmax = 224 nm, features which are typical for dpa derivatives. To establish the self-assembly behaviour of 1Gal with lanthanide Eu(III) and its ability to form complexes, a selfassembly titration was performed by adding aliquots of Eu(CF3SO3)3 to a 2 × 10 -5 M aqueous solution of 1Gal and monitoring changes in the UV-Vis absorbance and Eu(III)centred emission spectra (Figure S-24, ESI †). Changes in absorbance spectra were modest, with hyperchromic shift in the spectrum around the maximum at 223 nm and higher energies, and only slight increase in absorbance in the peak with λmax = 274 nm. Upon addition of Eu(III), the non-phosphorescent ligand sensitised metal-centred emission with characteristic line-like bands at 591, 614, 625 and 695 nm which correspond to 5 D0 → 7 F1-4 transitions, which increased in intensity with lanthanide ion concentration. Global stability constants were estimated by fitting spectroscopic data by non-linear regression (ReactLab Equilibria, Jplus Consulting Pty Ltd) to a model including the formation of Eu:1Galn (n = 1,3) self-assemblies in solution. When 1:2 assembly was included in the model, the fit did not converge. The ground state data indicated logβ1:1 = 6.4 and logβ1:3 = 16.1±0.2, while fitting data from the emission of the excited state broadly agreed, with logβ1:1 = 5.5 and logβ1:3 = 14.9±0.2. These stability constants with Eu(III) agree closely with those obtained with Tb(III) for related ligand structures by us and others. .