ICCAS OpenIR
One-Dimensional Ferromagnetically Coupled Bimetallic Chains Constructed with trans-[Ru(acac)(2)(CN)(2)](-): Syntheses, Structures, Magnetic Properties, and Density Functional Theoretical Study
Guo, Jun-Fang2; Wang, Xiu-Teng1; Wang, Bing-Wu1; Xu, Guan-Cheng1; Gao, Song1; Szeto, Lap3; Wong, Wing-Tak3; Wong, Wai-Yeung4; Lau, Tai-Chu2
2010
Source PublicationCHEMISTRY-A EUROPEAN JOURNAL
ISSN0947-6539
Volume16Issue:11Pages:3524-3535
AbstractFour cyano-bridged 1D bimetallic polymers have been prepared by using the paramagnetic building block trans-[Ru(acac)(2)(CN)(2)](-) (Hacac = acetylacetone): {[{Ni(tren)}-{Ru(acac)(2)(CN)(2)}][ClO4]center dot CH3OH}(n) (1) (tren = tris(2-aminoethyl)amine), {[{Ni(cyclen)}{Ru(acac)(2)(CN)(2)}][ClO4]center dot CH3OH}(n) (2) (cyclen = 1,4,7,10-tetraazacyclododecane), {[{Fe(salen)}{Ru(acac)(2)(CN)(2)}]}(n) (3) (salen(2-) =N,N'-bis(salicylidene)-o-ethyldiamine dianion) and [{Mn(5,5'-Me(2)salen)}(2){Ru(acac)(2)(CN)(2)}][Ru(acac)(2)(CN)(2)]center dot 2CH(3)OH (4) (5,5'-Me(2)salen = N,N'-bis(5,5'-dimethylsalicylidene)-o-ethylenediimine). Compounds 1 and 2 are 1D, zigzagged NiRu chains that exhibit ferromagnetic coupling between Ni-II and R-III ions through cyano bridges with J = + 1.92 cm(-1), zJ' = 1.37 cm(-1), g = 2.20 for 1 and J = + 0.85 cm(-1), zJ' = -0.16 cm(-1), g = 2.24 for 2. Compound 3 has a 1D linear chain structure that exhibits intrachain ferromagnetic coupling (J = + 0.62 cm(-1), zJ' = 0.09 cm(-1), g = 2.08), but antiferromagnetic coupling occurs between FeRu chains, leading to metamagnetic behavior with T-N = 2.6 K. In compound 4, two Mn-III ions are coordinated to trans-[Ru(acac)(2)(CN)(2)](-) to form trinuclear Mn2Ru units, which are linked together by pi-pi stacking and weak Mn center dot center dot center dot O* interactions to form a 1D chain. Compound 4 shows slow magnetic relaxation below 3.0 K with phi = 0.25, characteristic of superparamagnetic behavior. The Mn-III center dot center dot center dot R-III coupling constant (through cyano bridges) and the coupling constant (between the trimers) are +0.87 and +0.24 cm(-1), respectively. Compound 4 is a novel single-chain magnet built from Mn2Ru trimers through non-covalent interactions. Density functional theory (DFT) combined with the broken symmetry state method was used to calculate the molecular magnetic orbitals and the magnetic exchange interactions between Rum and M (M = Ni-II, Fe-III, and Me-III) ions. To explain the somewhat unexpected ferromagnetic coupling between low-spin Ru-III and high-spin Fe-III and Mn-III ions in compounds 3 and 4, respectively, it is proposed that apart from the relative symmetries, the relative energies of the magnetic orbitals may also be important in determining the overall magnetic coupling in these bimetallic assemblies.
KeywordCoordination Modes Density Functional Calculations Magnetic Properties Molecule-based Magnets Ruthenium Single-chain Magnets
DOI10.1002/chem.200902047
Indexed BySCI
Language英语
WOS IDWOS:000276058100029
PublisherWILEY-BLACKWELL
Citation statistics
Cited Times:64[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/70774
Collection中国科学院化学研究所
Corresponding AuthorGao, Song
Affiliation1.Peking Univ, Beijing Natl Lab Mol Sci, State Key Lab Rare Earth Mat Chem & Applicat, Coll Chem & Mol Engn, Beijing 100871, Peoples R China
2.City Univ Hong Kong, Dept Biol & Chem, Kowloon Tong, Hong Kong, Peoples R China
3.Univ Hong Kong, Dept Chem, Hong Kong, Hong Kong, Peoples R China
4.Hong Kong Baptist Univ, Dept Chem, Kowloon, Hong Kong, Peoples R China
Recommended Citation
GB/T 7714
Guo, Jun-Fang,Wang, Xiu-Teng,Wang, Bing-Wu,et al. One-Dimensional Ferromagnetically Coupled Bimetallic Chains Constructed with trans-[Ru(acac)(2)(CN)(2)](-): Syntheses, Structures, Magnetic Properties, and Density Functional Theoretical Study[J]. CHEMISTRY-A EUROPEAN JOURNAL,2010,16(11):3524-3535.
APA Guo, Jun-Fang.,Wang, Xiu-Teng.,Wang, Bing-Wu.,Xu, Guan-Cheng.,Gao, Song.,...&Lau, Tai-Chu.(2010).One-Dimensional Ferromagnetically Coupled Bimetallic Chains Constructed with trans-[Ru(acac)(2)(CN)(2)](-): Syntheses, Structures, Magnetic Properties, and Density Functional Theoretical Study.CHEMISTRY-A EUROPEAN JOURNAL,16(11),3524-3535.
MLA Guo, Jun-Fang,et al."One-Dimensional Ferromagnetically Coupled Bimetallic Chains Constructed with trans-[Ru(acac)(2)(CN)(2)](-): Syntheses, Structures, Magnetic Properties, and Density Functional Theoretical Study".CHEMISTRY-A EUROPEAN JOURNAL 16.11(2010):3524-3535.
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