Self-assembly of the first discrete 3d-4f-4f triple-stranded helicate

Article Article scientifique Article Self-assembly of the first discrete 3d-4f-4f triple-stranded helicate eng 2009 author Riis-Johannessen Thomas 648914 author Bernardinelli Gérald Hugues 24765 author Filinchuk Yaroslav 530008 author Clifford Sarah Elizabeth 669086 author Dalla Favera Natalia author Piguet Claude 0000-0001-7064-8548 22415 5512-5525 10.1021/ic900654m 19499959 1520-510X 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(II) (3d-block) and Lu(III) (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(2)Lu(2)(L5)(2)](10+). Interestingly, the removal of Zn(II) from the former triple-helical complex has only a minor effect on the coordination of Lu(III), 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 A) and long-range (ca. 18 A) intramolecular intermetallic d-f and f-f interactions. Dewey 540 40 Département de chimie minérale, analytique et appliquée 145 false Inorganic chemistry 48 12 8d110232-05b9-47be-ad06-b115239b4e69 Article (Accepted version) Restricted article.pdf 1767691 application/pdf restrictedAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie minérale, analytique et appliquée

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Self-assembly of the first discrete 3d-4f-4f triple-stranded helicate	Inorganic chemistry			2009	579	9

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Clifford, Sarah Elizabeth