Solid-stateversussolution investigation of a luminescent chiral BINOL-derived bisphosphate single-molecule magnet

Abstract

The enantiopure coordination polymer [Dy(hfac)3((S/R)-L)]n ([(S/R)-1]n) involving a BINOL-derived bisphosphate ligand (S/R)-L is investigated both in solution and solid-state.

Circularly polarized luminescence of Eu(III) complexes with chiral 1,1′‐bi‐2‐naphtol‐derived bisphosphate ligands

“…However, the most intense ECD signals for [(S/R)-3] and [(S,S,S/R,R,R)-4] are expected at a higher energy which are out from the experimental energy range. Similarly to what was observed for [Dy (hfac) 3 ((S)/(R)-L 1 )] and [Dy(hfac) 3 ((S,S,S)/(R,R,R)-L 3 )], 51,52 the ECD signals centered at 30,000 cm À1 (333 nm) and 34,000 cm À1 (294 nm) for (S)/(R)-L 1 and (S,S,S)/(R, R,R)-L 3 are exalted after the coordination of the achiral Eu(hfac) 3 unit in [(S/R)-1] and [(S/R)-3]. The same is not observed for [(S,S,S/R,R,R)-2] and [(S,S,S/R,R,R)-4].…”

“…The UV‐visible absorption and ECD spectra for the complexes [( S/R )‐1] , [( S , S , S/R , R , R )‐2] , [( S/R )‐3] , and [( S , S , S/R , R , R )‐4] in CH 2 Cl 2 solution are presented in Figures S15–S18. It was previously demonstrated by NMR studies and density functional theory (DFT) calculations that the coordination polymer {[Eu(hfac) 3 ( S / R ‐L 1 )]} n is fragmented to monomeric species by its solubilization 51 . The suggested structure of the monomeric specie is depicted in Figure S19.…”

“…n is fragmented to monomeric species by its solubilization. 51 The suggested structure of the monomeric specie is depicted in Figure S19. The fragmentation of the polymeric structure is accompanied with a reorganization of both hfac À anions and binaphtyl-based ligand.…”

Field-Induced Single-Molecule Magnets of Dysprosium Involving Quinone Derivatives

“…The compounds 1 and 2 displayed a magnetic relaxation mainly through a pure Raman process (Figure 4, Figure 6 and Figure S9), which could be justified by the applied magnetic field (cancelling of the QTM), the moderate value of the field (the direct process is not the fastest magnetic relaxation process) and the low temperature range at which the relaxation times are extracted (below 10 K), leading to a negligible Orbach contribution. Recently, several Dy III -based SMMs displaying pure Raman magnetic relaxation under moderate applied field in the low temperature range have been reported [43][44][45][46][47][48][49]. For some of the reported example in Table 1, an Orbach process can be involved in the magnetic relaxation in the high temperature range, in which an out-of-phase contribution of the magnetic susceptibility was measured.…”

Chiral or Luminescent Lanthanide Single-Molecule Magnets Involving Bridging Redox Active Triad Ligand

“…In a general manner, the addition of one or more physical properties to the SMM behavior paves the way to the design of multi-properties SMM as well as the study of a possible synergy between the different properties. Moreover, when chirality is added to the (luminescent) SMM behavior [21][22][23][24][25][26][27][28], chiral SMM [29], ferroelectric SMM [30] as well as chiral luminescent SMM [31][32][33][34][35][36] and magneto-chiral SMM [37,38] can be obtained. To these three properties, the introduction of redox-active ligands is of interest because it could permit to switch both optical and magnetic properties depending on the oxidation state of the ligand [39][40][41][42][43][44][45][46].…”