Complexes 1, 2, and 4 crystalize in monoclinic C 2/c, tetragonal I-4, and triclinic P-1 space groups, respectively, and significantly differ in their crystal packing. Close inspection of their crystal structures shows the prominent influence of the character of N-substituents on the complexes' self-assembly and intermolecular non-covalent interactions. Hershfield surface analysis is useful in the analysis of crystal packing of molecules and interactions between them. This analysis unveils that intermolecular contacts for the title compounds are dominated by H•••H contacts that range from 69 to 76%, indicating the significant contribution of van der Waals interactions to their self-assembly (Figures and). These weak forces are further affected by more specific intermolecular The photophysical properties of 1-4 in solution and as powders were explored by UV-Vis absorption and photoluminescence (PL) spectroscopy (Figure , top) and results are summarised in Table . In a dilute degassed toluene solution, all compounds feature a major absorption band at 336-358 nm. Additionally, for 3 and 4, which both bear N-bonded phenyl, an intensive absorption band at 289-290 nm appears. For both alkylaluminium derivatives of N-phenylanthranilic acid, the absorption properties do not differ if the alkyl substituent is modified. The influence of solvents such as benzene, DCM THF was investigated for 4 (Figure -26), and it revealed recognisable solvatochromism only in the case of THF as an oxygen donor solvent; the respective DOSY experiment (for details, see Figure and Table ) indicates that THF does not coordinate to the Al centers but likely solvates the outer-sphere by C-Haryl•••O noncovalent interactions. The solid-state spectra of the studied compounds display broad absorption bands in the range from 300 to 450 nm.