Photoluminescent Lanthanide(III) Single‐Molecule Magnets in Three‐Dimensional Polycyanidocuprate(I)‐Based Frameworks

Abstract

Three‐dimensional bimetallic cyanido‐bridged frameworks, [LnIII(2,2′‐bipyridine N,N′‐dioxide)2(H2O)][CuI2(CN)5]⋅5 H2O (Ln=Dy, 1; Yb, 2), are reported. They exhibit the effect of slow relaxation of magnetization, leading to a magnetic hysteresis loop, and sensitized visible‐to‐near‐infrared photoluminescence. Both physical properties are related to the eight‐coordinated lanthanide(III) complexes embedded in the unprecedented coordination skeleton composed of symmetry‐breaking polycyanidocuprate linkers. The three‐dimensional d–f cyanido‐bridged network was shown to serve as an efficient coordination scaffold to achieve emissive lanthanide single‐molecule magnets.

Holmium(iii) molecular nanomagnets for optical thermometry exploring the luminescence re-absorption effect

“…3). [19][20][21][22][23][24][25][26][27] However, the comparison of the low-(10 K) and high-temperature (300 K) re-absorption patterns agrees well with the calculated energy splitting of the ground multiplet determined from the ab initio calculations, including both the energy positions of the maxima related to the groups of closely lying excited states as well as the overall energy of the crystal eld splitting for the ground multiplet, slightly exceeding 300 cm À1 (Fig. S34, and detailed discussion in the ESI †).…”

Mixed Tb/Dy coordination ladders based on tetra(carboxymethyl)thiacalix[4]arene: a new avenue towards luminescent molecular nanomagnets

“…Thus, the last value expected for lanthanide-based SMMs would be located in the 2-9 range. 39 As several examples of SMMs lacking the Orbach process have been reported, 84 we tried to t the temperature dependence of the relaxation times excluding Orbach process; however, it was not possible to obtain a satisfying t.…”

Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets

“…Alternatively, luminescent molecular nanomagnets can be obtained by the incorporation of lanthanide ions into coordination frameworks, including metal–organic frameworks 36 , 37 , based on organic linkers or d-block metalloligands 38 – 40 . The up-to-date reported routes toward emissive SMMs explore rather sophisticated lanthanide(III) moieties exploring complicated organic ligands or a multi-component approach demanding the second metal complex 18 , 39 , 40 . Therefore, there is an attractive perspective in searching for simpler organic or inorganic molecular systems involving lanthanide(III) centers that can serve as luminescent molecular nanomagnets.…”