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cyano-bridged Ln^3＋-Cr^3＋ Binuclear Complexes [Ln（L）x（H2O）y^- Cr（CN）6]·mL·nH2O （Ln=La-Nd, x=5, y=2, m=1 or 2, n=2 or 2.5; Ln-Sm-Dy, Er, x=4, y=3, m=0, n=1.5 or 2.0; L= 2-pyrrolidinone）： Structure, Magnetism and Spin Density Map

引用

Chinese Journal of Chemistry 2007年第3期25卷 329-336页

作者：孙献茹陈志达王明伟王炳武阎峰 CHEUNG Kung-Kai State Key Laboratory of Rare Earth Materials Chemistry and Applications College of Chemistry and Molecular Engineering Peking University Beijing 100871 China Department of Chemistry and PKU-HKU Joint Laboratory on Rare Earth Materials and Bioinorganic Chemistry the University of Hong Kong Pokfulam Road Hong Kong China

In order to shed light upon the nature and mechanism of 4f-3d magnetic exchange interactions, a series of binuclear complexes of lanthanide（3＋） and chromium（3＋） with the general formula [Ln（L）5（H2O）2Cr（CN）6]·mL· nH2O （Ln=La （1）, Ce （2）, Pr （3）, Nd （4）; x=5, y=2, m=1 or 2, n=2 or 2.5; L=2-pyrrolidinone） and [Ln（L）4（H2O）3Cr（CN）6] ·nH2O （Ln=Sm （5）, Eu （6）, Gd （7）, Tb （8）, Dy （9）, Er （10）; x=4, y=3, m=0, n= 1.5 or 2.0; L=2-pyrrolidinone） were prepared and the X-ray crystal structures of complexes 2, 6 and 7 were determined. All the compounds consist of a Ln-CN-Cr unit, in which Ln^3＋ in a square antiprism environment is bridged to an octahedral coordinated Cr^3＋ ion through a cyano group. The magnetic properties of the complexes 3 and 6-10 show an overall antiferromagnetic behavior. The fitting to the experimental magnetic susceptibilities of 7 give g= 1.98, J=0.40 cm^-1, zJ＇= -0.21 cm^-1 on the basis of a binuclear spin system （Scd=7/2, Scr=3/2）, revealing an intra-molecular Gd^3＋-Cr^3＋ ferromagnetic interaction and an inter-molecular antiferromagnetic interaction. For 7 the calculation of quantum chemical density functional theory （DFT）, combined with the broken symmetry approach, showed that the calculated spin coupling constant was 20.3 cm^-1, supporting the observation of weak ferromagnetic intra-molecular interaction in 7. The spin density distributions of 7 in both the high spin ground state and the broken symmetry state were obtained, and the spin coupling mechanism between Gd^3＋ and Cr^3＋ was discussed.

关键词： cyano-bridged compound 4f-3d magnetic coupling Ln-Cr spin density magnetic property

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Anions Tunable cyano-bridged Homospin Iron(Ⅱ)Single-Chain Magnet

Anions Tunable Cyano-Bridged Homospin Iron(Ⅱ)Single-Chain M...

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中国化学会第九届全国无机化学学术会议

作者： Dong Shao Xin-Yi Wang State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical EngineeringNanjing University

Since the first observation of the single-chain magnet(SCM)behaviour in a Co-nitroxide radical chain in 2001,SCMs have attracted great interest in the field of molecular *** the construction of SCMs,the interchain interactions seems more difficult to control than the magnetic anisotropy of spin units and the intrachain *** the extensive research of SCMs are reported in the literature,only limited systems study the tuning of interchain magnetic coupling in single-chain magnets which ascribe to the hardly controlling of interchain separation and the arrangement of the chains in the crystal packing. We prepared a SCM-based antiferromagnet and a pure cyano-bridged homospin SCM by using anions of different size,which represents the first example of tunable homospin SCM systems.

关键词： Smgle-cham magnet cyano-bridged compound interchain interactions anions tuning homospin

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