Lanthanide Loading of Luminescent Multi-Tridentate Polymers under Thermodynamic Control

Article Article scientifique Article Lanthanide Loading of Luminescent Multi-Tridentate Polymers under Thermodynamic Control eng 2014 author Babel Lucille author Hoang Thi Nhu Y 732852 author Nozary Homayoun 86105 author Salamanca Jasmina 733472 author Guenee Laure 115015 author Piguet Claude 0000-0001-7064-8548 22415 3568-3578 10.1021/ic4030525 0020-1669 This work illustrates the use of basic statistical mechanics for rationalizing the loading of linear multitridentate polymers with trivalent lanthanides, Ln(III), and identifies the specific ionic sizes of europium and yttrium as promising candidates for the further design of organized heterometallic f–f′ materials. Using [Ln(hfac)3] (hfac = hexafluoroacetylacetonate) as lanthanide carriers, the thermodynamically controlled formation of Wolf type-II lanthanidopolymers [{Ln(hfac)3}m(L4)] is modeled with the help of two simple microscopic descriptors: (i) the intrinsic affinity of Ln(III) for the tridentate binding sites fN3Ln and (ii) the intermetallic interactions ΔE1–2Ln,Ln operating between two occupied adjacent sites. Selective complexation (fN3La fN3Eu > fN3Y) modulated by anticooperative interactions (ΔE1–2La,La ΔE1–2Eu,Eu > ΔE1–2Y,Y ≈ 0) favors the fixation of Eu(III) in semiorganized lanthanidopolymers [{Eu(hfac)3}m(L4)] displaying exploitable light-downshifting. Dewey 540 40 Département de chimie minérale, analytique et appliquée 145 false Inorganic chemistry 53 7 9d53eb66-a0a1-4ed2-bf3d-e3c30675eb5e Article (Published version) Restricted C Piguet 0414B.pdf 2799454 application/pdf restrictedAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie minérale, analytique et appliquée

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Lanthanide Loading of Luminescent Multi-Tridentate Polymers under Thermodynamic Control	Inorganic chemistry			2014	652	3

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Salamanca, Jasmina