Closely Related Organometallic Er(III) Single-Molecule Magnets with Sizably Different Relaxation Times of Quantum Tunneling of Magnetization

Xue, Tianjiao1; Ding, You-Song1; Reta, Daniel2,3; Chen, Qi-Wei4; Zhu, Xiaofei4; Zheng, Zhiping1

2022-12-01

10.1021/acs.cgd.2c01177

CRYSTAL GROWTH & DESIGN   影响因子和分区

1528-7483

1528-7505

Single-molecule magnets (SMMs) are of interest for storage and quantum processing of information. Herein, we report three new SMMs, ([K(DME)2][Er(COTTBS2)2] (1), [K(18-C-6)(THF)2][Er(COTTBS2)2] (2), and [K(2,2,2-cryptand)][Er-(COTTBS2)2] (3)), each of which features an Er(III) ion sandwiched by two bis(mono-tert-butyldimethylsilyl) substituted cyclooctatetraenide (1,4-(tBuMe2Si)2C8H6 or COTTBS2) ligands, leading to uniaxial magnetic anisotropy. With the chemically identical complex anion of [Er(COTTBS2)2]-, these SMMs differ only in the specific complex form of the same counterion K+, namely, [K(DME)2]+ (DME = ethylene glycol dimethyl ether) in 1, [K(18-C-6)(THF)2]+ in 2, and [K(2,2,2-cryptand)]+ in 3. Magnetic studies reveal comparable blocking temperatures of around 10 K and similar energy barriers (193(10) K for 1, 171(10) K for 2, and 166(9) K for 3) for magnetization reversal. By using the vibrating sample magnetometry waveform method, the transformed AC frequency is down to 0.0004 Hz; this frequency is 4 orders of magnitude smaller than the usual instrumentation limit. Accurate measurement of the quantum tunnelling of magnetization (QTM) relaxation time (tau QTM) made possible at such a low frequency allows for confident assessment and comparison between closely related SMMs. For 1, 2, and 3, the tau QTM was found to be 17(1) s, 13(1) s, and 65(2) s, respectively. The multifold difference in tau QTM between 3 and 1 or 2 indicates that magnetic relaxation by QTM can be profoundly influenced by the nonmagnetic component and crystal environment of an SMM, and specifically the form of the counterion in the present case. Our findings thus suggest a new and different approach to tuning the QTM behavior and the overall characteristics of SMMs.

SCI ; EI

英语

第一 ; 通讯

National Natural Science Foundation of China["92261203","22101116","21971106"] ; Stable Support Plan Program of Shenzhen Natural Science Fund[20200925161141006] ; Shenzhen Fundamental Research Program[JCYJ20220530115001002] ; Postdoctoral Scientific Research Fund[K21217520]

Chemistry ; Crystallography ; Materials Science

Chemistry, Multidisciplinary ; Crystallography ; Materials Science, Multidisciplinary

WOS:000903680800001

AMER CHEMICAL SOC

20225213294790

Erbium compounds ; Ethylene ; Ethylene glycol ; Gadolinium compounds ; Ions ; Ligands ; Magnetic anisotropy ; Magnetic relaxation ; Molecules ; Organometallics ; Relaxation time

Magnetism: Basic Concepts and Phenomena:701.2 ; Physical Chemistry:801.4 ; Organic Compounds:804.1 ; Classical Physics; Quantum Theory; Relativity:931 ; Physical Properties of Gases, Liquids and Solids:931.2 ; Atomic and Molecular Physics:931.3

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Key Lab Rare Earth Chem, Dept Chem,Guangdong Higher Educ Inst 2022KSYS006, Shenzhen 518055, Guangdong, Peoples R China
2.Euskal Herriko Unibertsitatea UPV EHU, Dept Chem, Bilbao 48009, Spain
3.IKERBASQUE, Basque Fdn Sci, Donostia Int Phys Ctr DIPC, Bilbao 48009, Spain
4.Changchun Univ Technol, Sch Chem & Life Sci, Changchun 130012, Peoples R China

Xue, Tianjiao,Ding, You-Song,Reta, Daniel,et al. Closely Related Organometallic Er(III) Single-Molecule Magnets with Sizably Different Relaxation Times of Quantum Tunneling of Magnetization[J]. CRYSTAL GROWTH & DESIGN,2022,23(1):565-573.

Xue, Tianjiao,Ding, You-Song,Reta, Daniel,Chen, Qi-Wei,Zhu, Xiaofei,&Zheng, Zhiping.(2022).Closely Related Organometallic Er(III) Single-Molecule Magnets with Sizably Different Relaxation Times of Quantum Tunneling of Magnetization.CRYSTAL GROWTH & DESIGN,23(1),565-573.

Xue, Tianjiao,et al."Closely Related Organometallic Er(III) Single-Molecule Magnets with Sizably Different Relaxation Times of Quantum Tunneling of Magnetization".CRYSTAL GROWTH & DESIGN 23.1(2022):565-573.