Accessing Lanthanide‐to‐Lanthanide Energy Transfer in a Family of Site‐Resolved [Ln^IIILn^III′] Heterodimetallic Complexes

Abstract

The ligand H 3 L( 6-[3-oxo-3-(2-hydroxyphenyl)propionyl]pyridine-2-carboxylic acid), which exhibits two different coordination pockets, has been exploitedt oe ngender and study energy transfer (ET) in two dinuclear [Ln III Ln III ']a nalogueso fi nterest, [EuYb] and [NdYb]. Their structurala nd physical properties have been compared with newly synthesiseda nalogues featuring no possible ET ([EuLu],[ NdLu], and [GdYb]) and with the corresponding homometallic [EuEu] and[ NdNd] analogues,w hich have been previously reported. Photophysicald ata suggest that ET between Eu III and Yb III does not occur to as ignificant extent, whereas emission from Yb III originates from sensitisation of the ligand. In contrast, energy migration seems to be occurring betweent he two Nd III centres in [NdNd],a sw ell as in [NdYb],inwhich Yb III luminescenceisthus, in part, sensitised by ET from Nd. This study shows the versatility of this molecular platform to further the investigation of lanthanide-tolanthanide ET phenomena in defined molecular systems.

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

“…The preference of these sites for two metals of different sizes, respectively, was exploited to prepare a large series of dinuclear heterometallic lanthanide complexes of outstanding purity. 20,32,33 The remarkable selectivity of this system was corroborated by means of DFT calculations, confirming that larger separations in ionic radii favour the enthalpy of the segregation further. 32,34 In view of such properties, these molecules were studied as an excellent platform for the realization of 2-qubit quantum processors, furnishing good quantum coherence features, Rabi oscillations and fulfilling the basic requirements to act as CNOT or SWAP qugates.…”

Modulation of the magnetic and photophysical properties in 3d–4f and 4f–4f′ heterobimetallic complexes involving a tetrathiafulvalene-based ligand

“…8b). Based on the previous works 62–66 and on the much more resolved Yb( iii )-centered luminescence (Fig. 8c) once Nd( iii ) has been changed by a Pr( iii ) ion in 19 , the absence of Nd( iii )-centered emission in 17 might be an indication of an efficient Nd-to-Yb Energy Transfer (ET).…”

Distributive Nd-to-Yb Energy Transfer within Pure [YbNdYb] Heterometallic Molecules

“…We had previously demonstrated similar Yb-to-Nd ET within a related dinuclear [NdYb] complex with a rather modest efficiency in MeOH of around 10%. 72 To probe the Nd-to-Yb ET in the trinuclear analogue, an extensive photophysical investigation was carried out on the three complexes, both, in 10 -4 M solution (1:1 mixture of MeOH and DMSO) and in the solid state at room temperature and at 77 K. These studies included absorption, excitation, and emission spectra, as well as lifetime decay determinations. The main photophysical data are compiled in Table 1.…”

“…The energy transfer process from the excited states of Nd 3+ to Yb 3+ was studied following strategies previously reported by us on bimetallic coordination compounds. 72 The emission properties of the derivatives [YbLaYb] (2) and [LuNdLu] (3) were studied first to confirm the antenna effect of the ligands on the Yb 3+ and Nd 3+ centres, respectively, and study their luminescence characteristics.…”

“…The reason of this segregation is that the larger site features two 'O,N,O' (dipicolinate type) tridentate chelates and one 'O,O' diketonate pocket, whereas the smaller position involves one tridentate and two bidentate pockets. [69][70][71][72] More recently, we have reported that combining two ligands, both featuring dipicolinate (O,N,O) and diketonate (O,O) units (H2LA and H2LB, Fig. 1), produces a novel molecular architecture when mixed with certain combinations of two different Ln(NO3)3 salts positioning selectively both metals in a [Ln-Ln'-Ln] topology.…”