Molecular lanthanide single-ion magnets: from bulk to submonolayers

Dreiser, Jan

doi:10.1088/0953-8984/27/18/183203

Cited by 87 publications

(79 citation statements)

References 184 publications

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“…[8,9] To date only af ew endohedral fullerene SMMs have been reported, including Ln x Sc 3Àx N@C 80 (Ln = Dy,H o, x = 1, 2) [9a-d] and Dy 2 TiC@C 80 , [9e] which are all based on an I h -C 80 cage entrapping multiple rare-earth-metal ions that are fixed as atriangle along with the central non-magnetic ion (N or C). Fors uch clusterfullerene SMMs based on multiple metal centers,t heir magnetic properties are generally determined jointly by the entrapped individual paramagnetic…”

Section: Fullerenesareclosedcarboncageswithhollowinteriorsandmentioning

confidence: 99%

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Mononuclear Clusterfullerene Single‐Molecule Magnet Containing Strained Fused‐Pentagons Stabilized by a Nearly Linear Metal Cyanide Cluster

et al. 2017

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Fused-pentagons results in an increase of local steric strain according to the isolated pentagon rule (IPR), and for all reported non-IPR clusterfullerenes multiple (two or three) metals are required to stabilizet he strained fused-pentagons, making it difficult to access the single-atom properties.Herein, we report the syntheses and isolations of novel non-IPR mononuclear clusterfullerenes MNC@C 76 (M = Tb,Y ), in which one pair of strained fused-pentagon is stabilized by amononuclear cluster.The molecular structures of MNC@C 76 (M = Tb,Y)were determined unambiguously by single-crystal X-ray diffraction, featuring an on-IPR C 2v (19138)-C 76 cage entrapping an early linear MNC cluster,w hichi sr emarkably different from the triangular MNC cluster within the reported analogous clusterfullerenes based on IPR-obeying C 82 cages. The TbNC@C 76 molecule is found to be afield-induced singlemolecule magnet (SMM). Fullerenesareclosedcarboncageswithhollowinteriors,andsuch unique structures bring about intriguing physical and chemical properties.[1] Most fullerenes isolated during the past three decades are based on classical carbon cages composed of hexagons and pentagons only, [1,2] forw hich the stability is generally determined by the isolated pentagon rule (IPR) proposed by Kroto in the 1980s.[3] According to IPR, fusedpentagons result in an increase of local steric strain of ac arbon cage,t hus destabilizing the fullerene. [3,4] Stabilization of the strained fused-pentagon within an on-IPR fullerene cage has been fulfilled by either endohedral or exohedral derivatization.[4] In particular,f or endohedral fullerenes which are as pecial class of fullerene with an atom, ion, or cluster entrapped in the interior of carbon cage, [5] the strong coordination of the entrapped metal ion(s) with the fused-pentagon gives rise to an intramolecular electron transfer and consequently stabilization of the non-IPR endohedral fullerene. [4][5][6] Most of the non-IPR endohedral fullerenes reported to date are based on clusterfullerenes [7] owing to the feasibility of entrapping multiple metals in diverse forms of metal clusters,s uch as Sc 3 N@C 68 , [6a,b] Gd 3 N@C 2n (2n = 78, 82, 84), [6c-e] LaSc 2 N@C 80 , [6f] and Sc 2 S@C 72 .[6g] Noteworthy,f or these reported non-IPR clusterfullerenes,multiple (two or three) metal ions are required to stabilize simultaneously the charged metal clusters and the fused-pentagons.H ence,i ti sd esirable to synthesize novel non-IPR endohedral fullerenes containing mononuclear metal clusters.Clusterfullerenes have been recently recognized as single molecule magnets (SMMs) with potential applications in spintronics,q uantum computing,a nd high-density storage devices. [8,9] To date only af ew endohedral fullerene SMMs have been reported, including Ln x Sc 3Àx N@C 80 (Ln = Dy,H o, x = 1, 2) [9a-d] and Dy 2 TiC@C 80 , [9e] which are all based on an I h -C 80 cage entrapping multiple rare-earth-metal ions that are fixed as atriangle along with the central non-magnetic ion (N or C)...

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Section: Fullerenesareclosedcarboncageswithhollowinteriorsandmentioning

confidence: 99%

“…[8,9] To date only af ew endohedral fullerene SMMs have been reported, including Ln x Sc 3Àx N@C 80 (Ln = Dy,H o,…”

Section: Fullerenesareclosedcarboncageswithhollowinteriorsandmentioning

confidence: 99%

Mononuclear Clusterfullerene Single‐Molecule Magnet Containing Strained Fused‐Pentagons Stabilized by a Nearly Linear Metal Cyanide Cluster

et al. 2017

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“…Regarding SMMs, a fast-growing number of mononuclear 3d/4f compounds that display slow relaxation of the magnetization have recently been introduced [7][8][9]. In this regard, the use of external magnetic fields to cancel an often-present fast zero-field relaxation of the magnetization [10,11], as well as the observation www.mdpi.com/journal/magnetochemistry of frequency dependence in 3D mononuclear species with negative but also positive [12,13] zero-field splitting (D) values, have been key factors toward the development of the subject.…”

Section: Introductionmentioning

confidence: 99%

Comparative Magnetic Studies in the Solid State and Solution of Two Isostructural 1D Coordination Polymers Containing CoII/NiII-Curcuminoid Moieties

et al. 2016

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Two novel 1D coordination chains containing the curcuminoid (CCMoid) ligand 9Accm have been characterized: [Co II (9Accm) 2 (4,4´-bpy)] n (1) and [Ni II (9Accm) 2 (4,4´-bpy)] n (2). The two compounds were synthesized by solvothermal and microwave (MW) assisted techniques, respectively, and crystals of both systems were directly obtained from the mother solutions. Crystal structures of 1 and 2 prove that both systems are isostructural, with the ligands in a trans configuration. The two chains have been magnetically characterized in solution by paramagnetic 1 H NMR, where 1 displayed typical features from Co II systems, with spread out signals; meanwhile, 2 showed diamagnetic behaviour. The dissociation of the latest in solution and the stability of the "[Ni(9Accm) 2 ]" unit were proved by further experiments in C 5 D 5 N. Additional UV-Vis absorption and fluorescence studies in solution were performed using exclusively 1. In the solid state χ M T vs. T and M/Nµ B vs. H/T data were collected and fitted for 1 and 2; both systems display Ising plane anisotropy, with significant D values. System 1 presented slow relaxation of the magnetization, displaying frequency dependence in the in-phase/out-phase ac magnetic susceptibility data, when an external dc field of 0.2 T was applied. Finally, 1 was deposited on a HOPG (highly oriented pyrolytic graphite) substrate by spin-coating and analysed by AFM.

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“…For perfect D 4d local symmetry, the QTM should be completely suppressed. 27 The twist angles between the diagonals of the two tetrapyrrole coordination squares are associated with the molecular symmetry. In an ideal SAP coordination site with D 4d local symmetry, the ligand field potential provides only diagonal matrix elements, where no mixing among the «J z ª states occurs.…”

Section: Ligand Fields To Enhancementioning

confidence: 99%