Self-assembly of the first discrete 3d - 4f - 4f triple-stranded helicate
(2009) Inorganic Chemistry — Vol. 48, n° 12, p. 5512-5525 (2009)
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- Abstract
- The connection of an additional bidentate chelating unit at the extremity of a segmental bis-tridentate ligand in L5 provides an unprecedented sequence of binding sites for the self-assembly of heterometallic 3d - 4f triple-stranded helicates. Thorough thermodynamic and structural investigations in acetonitrile show the formation of intricate mixtures of complexes when a single type of metal (3d or 4f) is reacted with L5. However, the situation is greatly simplified when Zn(11) (3d-block) and Lu(111) (4f-block) are simultaneously coordinated to L5, thus leading to only two identified species: the target C 3-symmetrical trinuclear triple-stranded d - f - f helicate HHH-[ZnLu 2(L5) 3] 8+ and a tetranuclear double-stranded complex [Zn 2Lu 2(L5) 2] 10+. Interestingly, the removal of Zn(11) from the former triple-helical complex has only a minor effect on the coordination of Lu(111), and translational autodiffusion coefficients show a simple reduction of the length of the molecular rigid cylinder from L = 2.7 nm in HHH-[ZnLu 2(L5) 3] 8+ to L = 2.3 nm in HHH-[Lu 2(L5) 3] 6+. Finally, the complete thermodynamic picture provides five novel stability macroconstants containing information about short-range (ca. 9 Å) and long-range (ca. 18 Å) intramolecular intermetallie d - f and f - f interactions. © 2009 American Chemical Society.
- Affiliations
ESRF, Grenoble (France) Chimie
Citations
Riis-Johannessen, T., Bemardinelli, G., Filinchuk, Y., Clifford, S., Favera, N. D., & Piguet, C. (2009). Self-assembly of the first discrete 3d - 4f - 4f triple-stranded helicate. Inorganic Chemistry, 48(12), 5512-5525. https://doi.org/10.1021/ic900654m (Original work published 2009)