Single-Molecule Magnet with Thermally Activated Delayed Fluorescence Based on a Metallofullerene Integrated by Dysprosium and Yttrium Ions

Abstract

It is vital to construct luminescent single-molecule magnets (SMMs) and explore their applications in quantum computing technique and magneto-luminescence devices. In this work, we report a luminescent single-molecule magnet with thermally activated delayed fluorescence (TADF) based on metallofullerene DyY2N@C80. DyY2N@C80 was constructed by integrating dysprosium and yttrium ions into a fullerene cage. Magnetic results suggest that DyY2N@C80 exhibits magnetic hysteresis loops below 8 K originating from the Dy3+ ion. Moreover, DyY2N@C80 exhibits TADF originating from the Y3+-coordinated carbon cage, whose luminescence peak positions and peak intensities can be obviously influenced by Dy3+. Furthermore, a supramolecular complex of DyY2N@C80 and [12]­Cycloparaphenylene ([12]­CPP) was then prepared to construct a single-molecule magnet with multiwavelength luminescence. The effects of host–guest interaction on photoluminescence properties of DyY2N@C80 were disclosed. Theoretical calculations were also employed to illustrate the structures of DyY2N@C80 and DyY2N@C80⊂[12]­CPP.

Using internal strain and mass to modulate Dy⋯Dy coupling and relaxation of magnetization in heterobimetallic metallofullerenes DyM2N@C80and Dy2MN@C80(M = Sc, Y, La, Lu)

“…6a). Similar characteristics of magnetic hysteresis were obtained for DyY 2 N@C 80 in the recent report by Wang et al 30 Magnetic hysteresis of Dy 2 YN@C 80 remains open up to 5 K. Likewise, the hysteresis without distinct QTM features is measured for Dy 2 LaN@C 80 up to 4 K (Fig. 7a).…”

“…9). An alternative fit with the Orbach mechanism gave = 𝑛 𝜏 0 3.0±0.5 s −1 and = 21.3±0.6 K, similar to the values reported by Wang et al, 30 but the agreement with 𝑈 eff the experimental data is worse than for the Raman mechanism. Note that the removal of the QTM part from Eq.…”

“…Indeed, TADF was recently reported in DyY 2 N@C 80 . 30 This result was very intriguing since the presence of Dy in the endohedral cluster was expected to increase the spin-orbit coupling and quench the fullerene-based radiative process. As the Ref.…”

Carbon cage isomers and magnetic Dy⋯Dy interactions in Dy2O@C88 and Dy2C2@C88 metallofullerenes

“…54,55,57,59,83 Counterintuitively, this conclusion is not directly transferable to analogous mono-nuclear Dy-EMFs. The hysteresis closing temperature in DySc 2 N@C 80 , 45,84 DyLu 2 N@C 80 , 60 DyY 2 N@C 80 , 85 DyScS@C 82 , 86 and DyYTiC@C 80 58 is near 7–8 K irrespective of their non-metal units. The synthesis and studies of mixed-metal oxide and carbide clusterfullerenes with single Dy atom, such as DyScO@C 82 and DyScC 2 @C 82 , and the studies of mono-nuclear Dy-SMMs with different cage sizes will be required to fully disclose this phenomenon.…”

Visible and near-infrared photoluminescence of a supramolecular complex constructed from a cycloparaphenylene nanoring and an erbium metallofullerene

“…17 Upon the formation of the supramolecular complex of DyY 2 N@C 80 ⊂ [12]CPP, the host-guest interaction reduces the effect of Dy 3+ on the photoluminescence of the carbon cage to some extent. 18 In the meantime, there is also a strong hostguest interaction between Ce 2 @D 5 -(450)-C 100 and [12]CPP. 19 Moreover, the cycloparaphenylenes are the structural units of carbon nanotubes with annular π-conjugated structures and unique photophysical properties.…”