Air-stable redox-active nanomagnets with lanthanide spins radical-bridged by a metal-metal bond

被引：126

作者：

Liu, Fupin ^{[1
]}

Velkos, Georgios ^{[1
]}

Krylov, Denis S. ^{[1
]}

Spree, Lukas ^{[1
]}

Zalibera, Michal ^{[2
]}

Ray, Rajyavardhan ^{[1
,3
]}

Samoylova, Nataliya A. ^{[1
]}

Chen, Chia-Hsiang ^{[1
]}

Rosenkranz, Marco ^{[1
]}

Schiemenz, Sandra ^{[1
]}

Ziegs, Frank ^{[1
]}

Nenkov, Konstantin ^{[1
]}

Kostanyan, Aram ^{[4
]}

Greber, Thomas ^{[4
]}

Wolter, Anja U. B. ^{[1
]}

Richter, Manuel ^{[1
,3
]}

Buechner, Bernd ^{[1
]}

Avdoshenko, Stanislav M. ^{[1
]}

Popov, Alexey A. ^{[1
]}

机构：

[1] Leibniz Inst Solid State & Mat Res IFW Dresden, Helmholtzstr 20, D-01069 Dresden, Germany

[2] Slovak Univ Technol Bratislava, Inst Phys Chem & Chem Phys, Radlinskeho 9, Bratislava 81237, Slovakia

[3] Tech Univ Dresden, Dresden Ctr Computat Mat Sci DCMS, D-01062 Dresden, Germany

[4] Phys Inst Univ Zurich, Winterthurerstr 190, CH-8057 Zurich, Switzerland

来源：

NATURE COMMUNICATIONS | 2019年 / 10卷 / 1期

基金：

欧盟地平线“2020”; 瑞士国家科学基金会;

关键词：

EXCHANGE INTERACTION; MAGNETIC BLOCKING; AB-INITIO; SINGLE; ION; BARRIER; METALLOFULLERENES; GD-2-AT-C79N; RELAXATION; BEHAVIOR;

D O I：

10.1038/s41467-019-08513-6

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Engineering intramolecular exchange interactions between magnetic metal atoms is a ubiquitous strategy for designing molecular magnets. For lanthanides, the localized nature of 4f electrons usually results in weak exchange coupling. Mediating magnetic interactions between lanthanide ions via radical bridges is a fruitful strategy towards stronger coupling. In this work we explore the limiting case when the role of a radical bridge is played by a single unpaired electron. We synthesize an array of air-stable Ln(2)@C-80(CH2Ph) dimetallofullerenes (Ln(2) = Y-2, Gd-2, Tb-2, Dy-2, Ho-2, Er-2, TbY, TbGd) featuring a covalent lanthanide-lanthanide bond. The lanthanide spins are glued together by very strong exchange interactions between 4f moments and a single electron residing on the metal-metal bonding orbital. Tb-2@C-80(CH2Ph) shows a gigantic coercivity of 8.2 Tesla at 5 K and a high 100-s blocking temperature of magnetization of 25.2 K. The Ln-Ln bonding orbital in Ln(2)@C-80(CH2Ph) is redox active, enabling electrochemical tuning of the magnetism.

引用

页数：11

共 46 条

[31] Negative cooperativity upon hydrogen bond-stabilized O2 adsorption in a redox-active metal-organic framework
Oktawiec, Julia
Jiang, Henry Z. H.
Vitillo, Jenny G.
Reed, Douglas A.
Darago, Lucy E.
Trump, Benjamin A.
Bernales, Varinia
Li, Harriet
Colwell, Kristen A.
Furukawa, Hiroyasu
Brown, Craig M.
Gagliardi, Laura
Long, Jeffrey R.
NATURE COMMUNICATIONS, 2020, 11 (01)
[32] Air-Stable Bifunctional HASPO Preligands for Metal-Catalyzed Cross-Couplings and Direct C-H Bond Arylations
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ISRAEL JOURNAL OF CHEMISTRY, 2010, 50 (5-6) : 652 - 663
[33] A family of lanthanide metal-organic frameworks based on a redox-active tetrathiafulvalene-dicarboxylate ligand showing slow relaxation of magnetisation and electronic conductivity
Hu, Jun-Jie
Li, Yu-Guang
Wen, He-Rui
Liu, Sui-Jun
Peng, Yan
Liu, Cai-Ming
DALTON TRANSACTIONS, 2021, 50 (41) : 14714 - 14723
[34] From Chiral Base Catalysts to Redox-Active Catalysts: Chasing the Identity of Metal Catalysts in Carbon-Carbon Bond-Forming Reactions
Kanai, Motomu
Matsunaga, Shigeki
Oisaki, Kounosuke
Shimizu, Yohei
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 2013, 71 (05) : 433 - 442
[35] Catalytic Synthesis of N-Heterocycles via Direct C(sp3)-H Amination Using an Air-Stable Iron(III) Species with a Redox-Active Ligand
Bagh, Bidraha
Broere, Daniel L. J.
Sinha, Vivek
Kuijpers, Petrus F.
van Leest, Nicolaas P.
de Bruin, Bas
Demeshko, Serhiy
Siegler, Maxime A.
van der Vlugt, Jan Ivar
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (14) : 5117 - 5124
[36] Highly Stable Metal-Organic Framework with Redox-Active Naphthalene Diimide Core as Cathode Material for Aqueous Zinc-Ion Batteries
Liu, Yongyao
Li, Zhonglin
Han, Yuejiang
Ji, Zhenyu
Li, Hengbo
Liu, Yuanzheng
Wei, Yifan
Chen, Cheng
He, Xiang
Wu, Mingyan
CHEMSUSCHEM, 2023, 16 (07)
[37] Redox-Active Metal-Organic Frameworks: Highly Stable Charge-Separated States through Strut/Guest-to-Strut Electron Transfer
Sikdar, Nivedita
Jayaramulu, Kolleboyina
Kiran, Venkayala
Rao, K. Venkata
Sampath, Srinivasan
George, Subi J.
Maji, Tapas Kumar
CHEMISTRY-A EUROPEAN JOURNAL, 2015, 21 (33) : 11701 - 11706
[38] Redox-active polymers based on nonbridged metal-metal bonds.: Electrochemical formation of [Os(bpy)(CO)(L)]n (bpy=2,2′-bipyridine;: L = CO, MeCN) and of their reduced forms:: A spectroelectrochemical study
Hartl, F
Mahabiersing, T
Chardon-Noblat, S
Da Costa, P
Deronzier, A
INORGANIC CHEMISTRY, 2004, 43 (22) : 7250 - 7258
[39] TETRAKIS(HYDROGEN-PHOSPHATO)DIMOLYBDENUM ION[MO2(HPO4)4]2- - COMPOUNDS WITH A METAL-METAL TRIPLE BOND WHICH ARE EASILY PREPARED AND PERMANENTLY STABLE IN AIR
BINO, A
COTTON, FA
INORGANIC CHEMISTRY, 1979, 18 (12) : 3562 - 3565
[40] A Series of Diamagnetic Pyridine Monoimine Rhenium Complexes with Different Degrees of Metal-to-Ligand Charge Transfer: Correlating 13CNMR Chemical Shifts with Bond Lengths in Redox-Active Ligands
Sieh, Daniel
Kubiak, Clifford P.
CHEMISTRY-A EUROPEAN JOURNAL, 2016, 22 (30) : 10638 - 10650

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