Controlled Heterometallic Composition in Linear Trinuclear [LnCeLn] Lanthanide Molecular Assemblies

Abstract

The combination of two different β-diketone ligands facilitates the size-controlled assembly of pure heterometallic [LnLn'Ln] linear compounds thanks to two different coordination sites present in the molecular scaffold.[HoCeHo], [ErCeEr] and [YbCeYb] analogues are presented here and are characterized both in the solid state and solution, demonstrating the selectivity of thi s unique method to produce heterometallic 4f molecular entities.

Formation of Heteropolynuclear Lanthanide Complexes Using Macrocyclic Phosphonated Cyclam-Based Ligands

“…Despite this, heteropolymetallic architectures have been prepared via statistical approaches, 14,15 by thermodynamic control of the coordination at specific sites 30,31 or by refined approaches including post-synthetic modification strategies, 32,33,34,35,36 orthogonal ligand deprotection, 37 or through careful ligand design, which can resolve these minor differences. 38,39,40…”

Unparalleled selectivity and electronic structure of heterometallic [LnLn′Ln] molecules as 3-qubit quantum gates

“…37 We show in this paper a theoretical analysis concluding that for this molecular architecture, the thermodynamically controlled selectivity in distributing different Ln metals at predetermined positions is unparalleled. For this study, we have performed density functional theory (DFT) based calculations on a novel member of the series with metal composition [ErPrEr] (1), presented here, as well as on the reported analogues 36,37 [HoCeHo] (2), [ErCeEr] (3), [YbCeYb] (4), [LuCeLu] (5) and [ErLaEr] (6). The suitability as multiqubit quantum gates of these molecules is assessed through a combination of appropriate techniques.…”

Design of pure heterodinuclear lanthanoid cryptate complexes

“…Lanthanide (Ln) molecular materials have attracted strong interest and have been intensively studied in a wide range of areas such as catalysis, [1][2][3][4][5] bioinorganic chemistry, 6,7 Magnetic Resonance Imaging, [8][9][10] luminescent materials, [11][12][13][14] multimodal imaging probes, [15][16][17] Single-Molecule Magnets (SMMs) [18][19][20][21] and Quantum Information Processing (QIP). [22][23][24][25][26][27][28][29][30][31][32][33][34] Many of the interesting properties of Ln complexes originate from their special electronic structure, where the 4f subshell is shielded from the environment by the 5s and 5p orbitals. 35 For example, this results in a large unquenched orbital-angular momentum which has been essential to build SMMs [36][37][38] with record blocking temperatures, [39][40][41] and leads to sharp absorption and emission bands, due to the lower inuence of vibrations on the f-f transitions.…”

“…[74][75][76] An elegant strategy relying on size selection of dissymmetric ligands has been employed to synthesise heteronuclear Ln complexes without scrambling. 31,33 However, this is only efficient when the included Ln(III) ions are of very different size, greatly limiting the choice of possible combinations. 67 We present herein a synthetic strategy for the realization of pure heterodinuclear Ln complexes of composition not limited by size selectivity.…”