Lanthanide Loading of Luminescent Multi-Tridentate Polymers under Thermodynamic Control

Babel, Lucille; Hoang, Thi Nhu Y; Nozary, Homayoun; Salamanca, Jasmina; Guenee, Laure; Piguet, Claude

doi:10.1021/ic4030525

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Title		Lanthanide Loading of Luminescent Multi-Tridentate Polymers under Thermodynamic Control
Authors		Babel, Lucille Hoang, Thi Nhu Y Nozary, Homayoun Salamanca, Jasmina Guenee, Laure Piguet, Claude
Published in		Inorganic chemistry. 2014, vol. 53, no. 7, p. 3568-3578
Abstract		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.
Identifiers		DOI: 10.1021/ic4030525
Full text		Article (Published version) (2.7 MB) - Limited access to UNIGE
Structures		Faculté des sciences / Section de chimie et biochimie / Département de chimie minérale, analytique et appliquée
Citation (ISO format)		BABEL, Lucille et al. Lanthanide Loading of Luminescent Multi-Tridentate Polymers under Thermodynamic Control. In: Inorganic Chemistry, 2014, vol. 53, n° 7, p. 3568-3578. doi: 10.1021/ic4030525 https://archive-ouverte.unige.ch/unige:35931