In this work, we focus on anthranilic acid (anth-H2) and its Nsubstituted derivatives, methyl (Me-anth-H2) or phenyl (Ph-anth-H2), as model proligands. The reaction between each of these acids and 1 eq. of the appropriate R3Al compound in toluene has resulted in the formation of a series of aluminium-stereogenic tetranuclear complexes [(anth)AlMe]4 (1), [(Me-anth)AlEt]4 (2) and [(Ph-anth)AlR]4 (where R = Me (3) or Et (4), Scheme 1) as yellow (for 1 and 2) or limegreen (for 3 and 4) crystalline powders in good yield. The resulting compounds are stable solids under an inert atmosphere but slowly decompose in the presence of moisture. They were characterised by elemental analysis, and NMR and FTIR spectroscopies. Single crystals of 1, 2 and 4 were obtained by recrystallisation from toluene or dichloromethane (DCM), and their identity was further confirmed by X-ray diffraction analysis (SCXRD). The 1 H NMR spectra of freshly dissolved compounds 1-4 confirm double deprotonation of the anthranilic acid (derivatives) in accordance with the stoichiometry of the reaction and include signals from both the alkylaluminium units and the corresponding carboxylate scaffold. Each compound displays two sets of signals indicating the presence of two different entities (for detailed spectroscopic characterisation of compounds 1-4, see SI). This is exemplified by compound 4 dissolved in C6D6 at ambient temperature (hereafter the most extensively studied compound due to its unique photoluminescence properties), where the aliphatic region of 1 H spectrum exhibits methyl triplets at 0.95 and 1.27 ppm (assigned 4 and 4´, respectively, see below) as well as two wellseparated resonances for methylene protons; a quartet at 0.40 ppm and what we attribute to a doubled eight-line pattern at -0.14 ppm. The latter multiplet suggests diastereotopic methylene protons, which clearly indicates the chiral nature of the aluminium centres, resulting from aggregation. Interestingly, the spectrum of 4 freshly dissolved in toluene-d8 at -70°C displays a single set of signals for the -AlCH2CH3 protons, which allows the explicit identification of the parent tetrameric form (Figure ). Similarly, the lowfield methylene signal is now absent, and the slightly broadened remaining methylene multiplets are well separated and appear at -0.22 and 0.01 ppm. Upon gradual heating up to 10°C, only a merging of these latter signals is observed and an increase in their intensity along with their slight shift to the high field. Interestingly, at 20°C new multiplet signals evolve which we attribute to a trimeric form 4´ (Figure , for a diffusional-ordered experiments, DOSY, vide infra). The presence of a quartet for the -AlCH2CH3 protons of the trimer 4´ indicates the presence of dynamic processes at higher temperatures To gain a more in-depth insight into the character of the anticipated two different aggregates of the [(R´-anth)AlR]4 series in solution, DOSY studies were performed for compounds 2-4 (for details, see SI). The data confirm that the tetrameric form is retained upon dissolution at lower temperatures. However, after a few hours of storage at ambient temperature, they gradually transform to the trimeric form, reaching a tetramer/trimer ratio ca. 2/1. The FTIR spectra of 1-4 display essentially identical patterns in the region around 1614-1553 and 1406-1403 cm -1 , which is typical for the νasym(CO2) and νsym(CO2) frequencies, respectively, clearly indicating similar coordination of the aluminium centre by the carboxylate group in each case. The SCXRD analysis confirmed that the molecular forms of 1, 2, and 4 are essentially isostructural, but differ in terms of the supramolecular arrangement within the crystal lattice (for the description of supramolecular structures, vide infra). Each appears in the solid state as a novel pseudo-centrosymmetric tetranuclear cage with the chiral-at-metal centres adopting a similar CNOO´ coordination environment, which results in the alternate arrangement of monomeric (R)-and (S)-units. Thus, the configuration of the individual stereogenic centres within the arbitrarily selected molecule can be described as (R,S,R,S), which is typical for aggregates seamed from an even number of enantiomers. To our knowledge, the only dimethylaluminium derivative of racemic ethyl lactate monomeric units of the same configuration as the chiral centre in the chelating ligand associate with each other to give a racemic mixture of (R,R) and (S,S) diastereoisomers, rac-[Me2Al{(S*)-elac}]2 (where elac = ethyl lactate). The four R´-anth ligands within the macrocycles reported here adopt µ2-ν2(N,O):ν 1 (O´) coordination modes by chelating one Al centre between carboxylic and amino groups and bridging the second Al centre utilizing the remaining carbonyl oxygen atom (Figure ). The Al-N distances within the series of reported compounds vary in the narrow range of 1.832 -1.851 Å, depending on the character of the N-substituent in the ligand, increasing from H to Ph. The electron density within the carboxylate groups in compounds 1, 2, and 4 is essentially equally distributed, as evidenced by the nearly equal C-O bond lengths (1.281 -1.285 Å). The carboxylate group adopts the syn-anti conformation commonly found in alkylaluminium derivatives of benzoic acid bearing additional donor ortho-functionalities. and the Al-O bonds within the 6-membered {AlOC3N} macrocycles formed by the chelating moiety are significantly shorter (1.790 -1.799 Å) than the bridging Al-O bonds (1.807-1.830 Å).