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10 pags., 5 figs., 3 tabs. ; New aluminium-alkali metal heterometallic compounds using the bulky ligand OAr = 2,6-bis(diphenylmethyl)-4-tert-butylphenoxide have been synthesized and characterized. The species obtained, [MAlMe (OAr)] (M = Li(2a), Na(2b), K(2c)) and [MAlMe (OAr) ] (M = Li(3a), Na(3b), K(3c)), include some of the few heterobimetallic examples of aluminate complexes with O-donor ligands described so far. Their activity in polymerization towards a difunctional monomer, such as Glycidyl Methacrylate (GMA), was evaluated. The compounds were revealed to be able to polymerize the acrylate groups via vinyl polymerization. Interestingly, the homometallic counterparts [AlXMe(OAr)] (X = Cl, Me), previously described by us, are very active in ROP processes of GMA. The combined polymerization process using both catalysts has also been explored to obtain a polymeric material with an exciting macromolecular architecture. ; Financial support from Spanish Government (MINECO CTQ2014-58270-R), the Alcalá University, Spain (CCG2015/ EXP-039) and EU COST Action CA15106 (CHAOS) is gratefully acknowledged. Dr M. T. M. thanks the Universidad de Alcalá and Comunidad de Madrid for a Postdoctoral Research Contract. M. P. thanks the Universidad de Alcalá for a Predoctoral Fellowship.

8 pags., 3 figs., 5 tabs. -- This article is part of the themed collections: Supramolecular & Polymorphism and 1st International Conference on Noncovalent Interactions ; New halogen bonded networks containing the organometallic complexes [Ru(CNBu)(X)] (X = Cl, Br, I) have been prepared. Two different types of halogen donors have been explored, I and ICFI, to study the influence of the halogen bond donor on the parameters and the nature of the interaction. We have performed a combined experimental and theoretical study. In the results, the species with ICFI as a halogen bond donor show weaker interactions, as evidenced by the geometrical parameters and by the DFT calculations. In fact, it was not possible to isolate the HaB network containing the complex [Ru(CNBu)(I)] and ICFI. Furthermore, the studies show that the interaction for iodine has a higher covalent component than that for ICFI. ; Financial support from the Spanish Government (MINECO CTQ2014-58270-R and Factoría de Cristalización-ConsoliderIngenio (CSD2006-00015)) and Alcalá University, Spain (CCG2018/EXP-038) is gratefully acknowledged. J. R. acknowledges the financial support through the CSIC (Spain) – Project PIE201860E136.