The first self-assembled trimetallic lanthanide helicates driven by positive cooperativity

The segmental tris-tridentate ligand L7 reacts with stoichiometric quantities of Ln(III) (Ln = La-Lu) in acetonitrile to give the complexes [Ln(2)(L7)(3)](6+) and [Ln(3)(L7)(3)](9+). Formation constants point to negligible size-discriminating effects along the lanthanide series, but Scatchard plots suggest that the self-assembly of the trimetallic triple-stranded helicates [Ln(3)(L7)(3)](9+) is driven to completion by positive cooperativity, despite strong intermetallic electrostatic repulsions. Crystallization provides quantitatively [Ln(3)(L7)(3)](CF3SO3)(9) (Ln = La, Eu, Gd, Tb, Lu) and the X-ray crystal structure of [Eu-3(L7)(3)](CF3SO3)(9) (.) (CH3CN)(9) (.) (H2O)(2) (Eu3C216H226N48O35F27S9, triclinic, P (1) over bar, Z = 2) shows the three ligand strands wrapped around a pseudo-threefold axis defined by the three metal ions rigidly held at about 9 Angstrom. Each metal ion is coordinated by nine donor atoms in a pseudo-trigonal prismatic arrangement, but the existence of terminal carboxamide units in the ligand strands differentiates the electronic properties of the terminal and the central metallic sites. Photophysical data confirm that the three coordination sites possess comparable pseudo-trigonal symmetries in the solid state and in solution. High-resolution luminescence analyses evidence a low-lying LMCT state affecting the central EuN9 site, so that multi-metal-centered luminescence is essentially dominated by the emission from the two terminal EuN6O3 sites in [Eu-3(L7)(3) ](9+). New multicenter equations have been developed for investigating the solution structure of [Ln(3)(L7)(3)](9+) by paramagnetic NMR spectroscopy and linear correlations for Ln = Ce-Tb imply isostructurality for these larger lanthanides. NMR spectra point to the triple helical structure being maintained in solution, but an inversion of the magnitude of the second-rank crystal-field parameters, obtained by LIS analysis, for the LnN(6)O(3) and LnN(9) sites with respect to the parameters extracted for Eu-III from luminescence data, suggests that the geometry of the central LnN(9) site is somewhat relaxed in solution.