Origin of Long-Range Ferromagnetic Ordering in Metal-Organic Frameworks with Antiferromagnetic Dimeric-Cu(II) Building Units

被引：83

作者：

Shen, Lei ^{[1
,2
]}

Yang, Shuo-Wang ^{[1
]}

Xiang, Shengchang ^{[3
]}

Liu, Tao ^{[5
]}

Zhao, Bangchuan ^{[6
,7
]}

Ng, Man-Fai ^{[1
]}

Goeettlicher, Joerg ^{[5
]}

Yi, Jiabao ^{[8
]}

Li, Sean ^{[8
]}

Wang, Lan ^{[6
]}

Ding, Jun ^{[9
]}

Chen, Banglin ^{[3
]}

Wei, Su-Huai ^{[4
]}

Feng, Yuan Ping ^{[2
]}

机构：

[1] Agcy Sci Technol & Res, Inst High Performance Comp, Singapore 138632, Singapore

[2] Natl Univ Singapore, Dept Phys, Singapore 117542, Singapore

[3] Univ Texas San Antonio, Dept Chem, San Antonio, TX 78249 USA

[4] Natl Renewable Energy Lab, Golden, CO 80401 USA

[5] Karlsruhe Inst Technol, Inst Synchrotron Radiat, D-76344 Eggenstein Leopoldshafen, Germany

[6] Nanyang Technol Univ, Sch Phys & Math Sci, Div Phys & Appl Phys, Singapore 637371, Singapore

[7] Chinese Acad Sci, Inst Solid State Phys, Hefei 230031, Anhui, Peoples R China

[8] Natl Univ Singapore, Dept Mat Sci & Engn, Singapore 117576, Singapore

[9] Univ New S Wales, Sch Mat Sci & Engn, Sydney, NSW 2052, Australia

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 41期

基金：

新加坡国家研究基金会; 美国国家科学基金会;

关键词：

HIGH H-2 ADSORPTION; HYDROGEN STORAGE; MOLECULAR-DYNAMICS; SEPARATION; SITES;

D O I：

10.1021/ja3077654

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Even though metal organic frameworks (MOFs) derived from antiferromagnetic dimeric-Cu(II) building units and nonmagnetic molecular linkers are known to exhibit unexpected ferromagnetic behavior, a comprehensive understanding of the underlying mechanism remains elusive. Using a combined theoretical and experimental approach, here we reveal the origin of the long-range ferromagnetic coupling in a series of MOFs, constructed from antiferromagnetic dimeric-Cu(II) building blocks. Our studies show that the strong localization of copper vacancy states favors spontaneous spin polarization and formation of local moment. These copper vacancy-induced moments are coupled via the itinerant electrons in the conjugated aromatic linkers to establish a long-range ferromagnetic ordering. The proposed mechanism is supported by direct experimental evidence of copper vacancies and the magnetic hysteresis (M-H) loops.

引用

页码：17286 / 17290

页数：5

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