The solution structure of homotrimetallic lanthanide helicates investigated with novel model-free multi-centre paramagnetic NMR methodsElectronic supplementary information (ESI) available: tables of structural factors Cikl, Dikl obtained for the model complexes and for [Ln3(L1)3]9+ in solution (Table S1) and geometrical factors calculated for the structure of [Eu3(L1)3]9+ optimized in the gas phase (Table S2). Figures showing a plot of 1/Tpara1i vs. according to eqn. (19) (Fig. S1), a plot of AFikl for the

Silver Baits for The “Miraculous Draught” of Amphiphilic Lanthanide Helicates

“…The X-ray crystal structure supports the formation of [La 2 Ag 2 (L12 C3 À2 H) 3 ]-A C H T U N G T R E N N U N G [OTf] 2 , which exists in the solid state as infinite linear polymers bridged by SAg-S bonds. In contrast, molecular dynamics (MD) simulations in the gas phase and in solution confirm the experimental diffusion measurements, which imply the formation of discrete molecular entities in these media, in which the sulfur atoms of each lipophilic ligand are rapidly exchanged within the Ag I coordination sphere.…”

“…Turned as a predictive tool, MD suggests that this Ag I templating effect is efficient only for n = 1-3, while for n > 3 very loose interactions occur between Ag I and the thioalkyl residues. The subsequent experimental demonstration that only 25 % of the total ligand speciation contributes to the formation of [Ln 2 Ag 2 (L12 C12 À2 H) 3 ] 2 + in solution puts the bases for a rational approach for the design of amphiphilic helical complexes with predetermined molecular interfaces.…”

“…Keywords: helical structures · heterometallic complexes · lanthanides · molecular dynamics · polynuclear complexes · silver for the UV sensitization of visible Eu III and Tb III emitters in the triple-stranded helicates [Ln 2 (L1) 3 ] 6 + , [Ln 3 (L2) 3 ] 9 + and [Ln 4 (L3) 3 ] 12 + . [7] However, the modern craze for profitable technological and/or (bio)medical applications of self-assembled lanthanide complexes introduced two additional criteria, which are difficult to fit simultaneously.…”

“…), the helical twist of the strands also induces unprecedented magnetic and luminescent properties when adequate open-shell d-block or f-block metals are considered. [2][3][4][5][6] In molecular magnetism, the ligand helicity is responsible for the existence of non-equivalent metalcentered paramagnetic g tensors, which is a prerequisite for building scalable quantum bits (qubits) for quantum information processing systems. [2][3][4] In photophysics, the minute modulation of the luminescent properties of trivalent lanthanides (Ln III ) in polynuclear helicates have been intensively exploited for the design of bioprobes with improved sensitivities, [5] and for the development of nanometric directional molecular light-converting devices.…”

“…[2][3][4] In photophysics, the minute modulation of the luminescent properties of trivalent lanthanides (Ln III ) in polynuclear helicates have been intensively exploited for the design of bioprobes with improved sensitivities, [5] and for the development of nanometric directional molecular light-converting devices. [6] In this context, the segmental oligo-tridentate ligands L1-L3 based on pyridinebenzimidazole patterns were early considered as attractive candidates because of 1) their easy synthetic access, 2) their helically twisted diphenylmethane spacers, and 3) the energies of their donor excited triplet states, which are suitable 3 ] 2 + complexes at millimolar concentration (Ln = La, Eu, Lu).…”