Infoscience

Thesis

Enantiopure helical (supra)molecular arrays containing lanthanides: design, synthesis and properties

The diastereoselective synthesis of chiral coordination compounds with d metals proved the effectiveness of the pinene-bipyridine approach in predetermining the chirality at the metal centre. The strong Lewis acidic character of lanthanide cations required the modification of this class of ligands in order to adapt their coordination properties to the binding affinity of Ln(III) toward hard donor atoms like oxygen. The pinene bipyridine carboxylic derivative (+)-L- (figure 1) has been designed and synthesized to form configurationally stable lanthanide complexes. This ligand proved its effectiveness as chiral building block for the synthesis of oligometallic supramolecular structures. Indeed a self-assembly process takes place with complete diastereoselectivity between the enantiomerically pure (-) or (+) L- and Ln(III) ions (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er) in methanol, giving rise to trinuclear enantiopure structures with general formula [Ln3(L)6(µ3-OH)(H2O)3](ClO4)2 , possessing predetermined helical chirality. The ligands in this case display a new version of supramolecular helical chirality since they are wrapping around a trimetallic core instead of one single metal centre. The same components afford a second polynuclear structure if the reaction is carried out in CH3CN. In this medium a three-dimensional tetranuclear array self-assembles (with general formula [Ln4(L)9(µ3-OH)](ClO4)2). The nine ligands are forming three distinct helical domains, two supramolecular as in the case of the trinuclear array and one classical around a single metal centre, with predetermined configuration. The two classes of compounds have been structurally characterized in solid state (X-ray and IR) and in solution (ES-MS, NMR). Their chiroptical properties were investigated by means of Circular Dichroism and Circularly Polarized Luminescence (for the emitting compounds). Trinuclear and tetranuclear arrays are shown to interconvert in CH3CN, in a process mediated by water. This process was rationalized taking into account the nature of the Ln(III) ions, the initial concentration of the components and the addition or removal of water in solution. The availability of both the enantiomers of the ligand prompted us to study the self-recognition capabilities of the two systems. 1H-NMR and CD studies reveal an almost complete chiral recognition in the self-assembly leading to the trinuclear complex. The process leading to tetranuclear species appears instead perturbed, probably due to the higher number of fundamental components involved (4 metals and 9 ligands instead of 3 metals and 6 ligands). Figure 1: Reaction conditions leading to the synthesis of trinuclear and tetranuclear Ln(III) complexes with ligand (+)-L-. The introduction of a carboxylic moiety onto the 6' posititon of the (-)-5,6- and (-)-4,5- pinene bipyridine lead to the tridentate ligands (-)-HL1 and (-)-HL2, respectively. Mononuclear neutral complexes are obtained upon reaction with Ln(ClO4)3. Different extents of diastereoselectivity are pointed out in the two systems by X-ray analysis and CD spectroscopy. In particular the ligand (-)-HL1, in which the pinene moiety is next to the binding site, seems to be more effective in predetermining the configuration at the metal centre. A low diastereoselectivity is instead expressed in the reactions with (-)-HL2 as revealed by the X-ray structure of [Pr{(-)-L2}3] (both Δ and Λ isomers detected) and by the CD spectrum void of signal.

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