Nanostructuring of Rare‐earth‐based Single‐Molecule Magnets as Long‐range Ordered Arrays in the Framework of Organic Metal Halide Perovskites

Abstract

The nanostructuring of single‐molecule magnets (SMMs) on substrates, in nanotubes and periodic frameworks is highly desired for the future magnetic recording devices. However, the ability to organize SMMs into long‐range ordered arrays in these systems is still lacking. Here, we report the incorporation of magnetic (RECl2(H2O)6)+ (RE=rare earths) molecular groups into the framework of an organic metal halide perovskite (OMHP)—(H2dabco)CsCl3. Intriguingly, we show the incorporated rare‐earth groups self‐organized into long‐range ordered arrays that uniformly and periodically distributed in the A sites of OMHP. The ordered (RECl2(H2O)6)+ groups serve as SMMs in the perovskite frameworks, exhibiting large effective magnetic moment, moderate magnetic anisotropy and two‐step relaxation behavior. With the additional merit of great structural flexibility and multifunction of OMHPs, the preparation of the first SMMs@OMHP magnetic materials furthers the development of molecular spintronics.

Ferroics in Hybrid Organic–Inorganic Perovskites: Fundamentals, Design Strategies, and Implementation

“…In HOIPs, magnetism can be introduced by incorporating unpaired magnetic elements, e.g., transition metal ions (Mn 2+ , Fe 2+ , Cr 2+ , and Cu 2+ ) or rare-earth ions (Eu 2+ , Gd 3+ , and Sm 3+ ), as B-site cations. [18][19][20][21][22][23]88] Although these magnetic elements can be doped into perovskite lattice to introduce magnetic properties, such tiny amounts of metal doping cannot form long-range ferromagnetic ordering (Figure 5a(i)). [89,90] Ferromagnetic HOIPs require magnetic metal ions to be embedded into corner-sharing BX 6 octahedral cages, whereby the bridged X-site halogens can act as a bridge to intermediate the superexchange interaction between next-nearest neighboring B-site ions (Figure 5a(ii)).…”

High, Multiple, and Nonvolatile Polarizations in Organic–Inorganic Hybrid [(CH3)3(CH2CH2Cl)N]2InCl5·H2O for Memcapacitor

“…From the perspective of facilitating ion migration, a variety of ionic conductors with small ionic radii such as proton (H + ), Li + , or Na + serve as candidates. − Among them, the proton stands out as the most attractive candidate due to its small size and its propensity to not form harmful metal dendrites that may block the migration pathways. Organic–inorganic metal halide hybrids are a new class of functional materials that usually consist of a relatively rigid inorganic framework and flexible organic motifs residing inside voids of the framework. − This structural feature allows a large structural tolerance and relatively weak interactions between anions and cations compared with pure organic or inorganic materials, providing ample space for long-range proton migration. Among these, the polyhedron with indium as central ions and halogen and water molecules as ligands [In X m (H 2 O) n , X = halogen anions, m + n = 6] are well known and have been extensively studied.…”