One-dimensional ferromagnetically coupled bimetallic chains constructed with trans-[Ru(acac)2(CN)2]-: Syntheses, structures, magnetic properties, and density functional theoretical study

Jun-Fang Guo; Xiu-Teng Wang; Bing-Wu Wang; Guan-Cheng Xu; Song Gao; Lap Szeto; Wing-Tak Wong; Wai-Yeung Wong; Tai-Chu Lau

doi:10.1002/chem.200902047

One-dimensional ferromagnetically coupled bimetallic chains constructed with trans-[Ru(acac)₂(CN)₂]^-: Syntheses, structures, magnetic properties, and density functional theoretical study

Jun-Fang Guo
, Xiu-Teng Wang
, Bing-Wu Wang
, Guan-Cheng Xu
, Song Gao
, Lap Szeto
, Wing-Tak Wong
, Wai-Yeung Wong
, Tai-Chu Lau

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

79 Citations (Scopus)

Abstract

Four 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]⋅CH₃OH}_n (1) (tren=tris(2‐aminoethyl)amine), {[{Ni(cyclen)}{Ru(acac)₂(CN)₂}][ClO₄]⋅ CH₃OH}_n (2) (cyclen=1,4,7,10‐tetraazacyclododecane), {[{Fe(salen)}{Ru(acac)₂(CN)₂}]}_n (3) (salen²⁻=N,N′‐bis(salicylidene)‐o‐ethyldiamine dianion) and [{Mn(5,5′‐Me₂salen)}₂{Ru(acac)₂(CN)₂}][Ru(acac)₂(CN)₂]⋅ 2 CH₃OH (4) (5,5′‐Me₂salen=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 Ru^III ions through cyano bridges with J=+1.92 cm⁻¹, z J′=−1.37 cm⁻¹, g=2.20 for 1 and J=+0.85 cm⁻¹, z J′=−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, z J′=−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 π–π stacking and weak Mn⋅⋅⋅O* interactions to form a 1D chain. Compound 4 shows slow magnetic relaxation below 3.0 K with ϕ=0.25, characteristic of superparamagnetic behavior. The Mn^III⋅⋅⋅Ru^III coupling constant (through cyano bridges) and the Mn^III⋅⋅⋅Mn^IIIcoupling 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 noncovalent 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 Ru^III and M (M=Ni^II, Fe^III, and Mn^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.

Original language	English
Pages (from-to)	3524-3535
Journal	Chemistry - A European Journal
Volume	16
Issue number	11
Online published	8 Mar 2010
DOIs	https://doi.org/10.1002/chem.200902047
Publication status	Published - 15 Mar 2010

Research Keywords

Coordination modes
Density functional calculations
Magnetic properties
Moleculebased magnets
Ruthenium
Singlechain magnets

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Guo, J.-F., Wang, X.-T., Wang, B.-W., Xu, G.-C., Gao, S., Szeto, L., Wong, W.-T., Wong, W.-Y., & Lau, T.-C. (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. https://doi.org/10.1002/chem.200902047

@article{8fd3ae5424874dc0a29a2d1eef181afd,

title = "One-dimensional ferromagnetically coupled bimetallic chains constructed with trans-[Ru(acac)2(CN)2]-: Syntheses, structures, magnetic properties, and density functional theoretical study",

abstract = "Four 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]⋅CH3OH\}n (1) (tren=tris(2‐aminoethyl)amine), \{[\{Ni(cyclen)\}\{Ru(acac)2(CN)2\}][ClO4]⋅ CH3OH\}n (2) (cyclen=1,4,7,10‐tetraazacyclododecane), \{[\{Fe(salen)\}\{Ru(acac)2(CN)2\}]\}n (3) (salen2−=N,N′‐bis(salicylidene)‐o‐ethyldiamine dianion) and [\{Mn(5,5′‐Me2salen)\}2\{Ru(acac)2(CN)2\}][Ru(acac)2(CN)2]⋅ 2 CH3OH (4) (5,5′‐Me2salen=N,N′‐bis(5,5′‐dimethylsalicylidene)‐o‐ethylenediimine). Compounds 1 and 2 are 1D, zigzagged NiRu chains that exhibit ferromagnetic coupling between NiII and RuIII ions through cyano bridges with J=+1.92 cm−1, z J′=−1.37 cm−1, g=2.20 for 1 and J=+0.85 cm−1, z J′=−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, z J′=−0.09 cm−1, g=2.08), but antiferromagnetic coupling occurs between FeRu chains, leading to metamagnetic behavior with TN=2.6 K. In compound 4, two MnIII ions are coordinated to trans‐[Ru(acac)2(CN)2]− to form trinuclear Mn2Ru units, which are linked together by π–π stacking and weak Mn⋅⋅⋅O* interactions to form a 1D chain. Compound 4 shows slow magnetic relaxation below 3.0 K with ϕ=0.25, characteristic of superparamagnetic behavior. The MnIII⋅⋅⋅RuIII coupling constant (through cyano bridges) and the MnIII⋅⋅⋅MnIIIcoupling 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 noncovalent 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 RuIII and M (M=NiII, FeIII, and MnIII) ions. To explain the somewhat unexpected ferromagnetic coupling between low‐spin RuIII and high‐spin FeIII and MnIII 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.",

keywords = "Coordination modes, Density functional calculations, Magnetic properties, Moleculebased magnets, Ruthenium, Singlechain magnets",

author = "Jun-Fang Guo and Xiu-Teng Wang and Bing-Wu Wang and Guan-Cheng Xu and Song Gao and Lap Szeto and Wing-Tak Wong and Wai-Yeung Wong and Tai-Chu Lau",

year = "2010",

month = mar,

day = "15",

doi = "10.1002/chem.200902047",

language = "English",

volume = "16",

pages = "3524--3535",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley \& Sons",

number = "11",

}

Guo, J-F, Wang, X-T, Wang, B-W, Xu, G-C, Gao, S, Szeto, L, Wong, W-T, Wong, W-Y & Lau, T-C 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, vol. 16, no. 11, pp. 3524-3535. https://doi.org/10.1002/chem.200902047

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-Fang; Wang, Xiu-Teng; Wang, Bing-Wu et al.
In: Chemistry - A European Journal, Vol. 16, No. 11, 15.03.2010, p. 3524-3535.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - One-dimensional ferromagnetically coupled bimetallic chains constructed with trans-[Ru(acac)2(CN)2]-

T2 - Syntheses, structures, magnetic properties, and density functional theoretical study

AU - Guo, Jun-Fang

AU - Wang, Xiu-Teng

AU - Wang, Bing-Wu

AU - Xu, Guan-Cheng

AU - Gao, Song

AU - Szeto, Lap

AU - Wong, Wing-Tak

AU - Wong, Wai-Yeung

AU - Lau, Tai-Chu

PY - 2010/3/15

Y1 - 2010/3/15

N2 - Four 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]⋅CH3OH}n (1) (tren=tris(2‐aminoethyl)amine), {[{Ni(cyclen)}{Ru(acac)2(CN)2}][ClO4]⋅ CH3OH}n (2) (cyclen=1,4,7,10‐tetraazacyclododecane), {[{Fe(salen)}{Ru(acac)2(CN)2}]}n (3) (salen2−=N,N′‐bis(salicylidene)‐o‐ethyldiamine dianion) and [{Mn(5,5′‐Me2salen)}2{Ru(acac)2(CN)2}][Ru(acac)2(CN)2]⋅ 2 CH3OH (4) (5,5′‐Me2salen=N,N′‐bis(5,5′‐dimethylsalicylidene)‐o‐ethylenediimine). Compounds 1 and 2 are 1D, zigzagged NiRu chains that exhibit ferromagnetic coupling between NiII and RuIII ions through cyano bridges with J=+1.92 cm−1, z J′=−1.37 cm−1, g=2.20 for 1 and J=+0.85 cm−1, z J′=−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, z J′=−0.09 cm−1, g=2.08), but antiferromagnetic coupling occurs between FeRu chains, leading to metamagnetic behavior with TN=2.6 K. In compound 4, two MnIII ions are coordinated to trans‐[Ru(acac)2(CN)2]− to form trinuclear Mn2Ru units, which are linked together by π–π stacking and weak Mn⋅⋅⋅O* interactions to form a 1D chain. Compound 4 shows slow magnetic relaxation below 3.0 K with ϕ=0.25, characteristic of superparamagnetic behavior. The MnIII⋅⋅⋅RuIII coupling constant (through cyano bridges) and the MnIII⋅⋅⋅MnIIIcoupling 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 noncovalent 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 RuIII and M (M=NiII, FeIII, and MnIII) ions. To explain the somewhat unexpected ferromagnetic coupling between low‐spin RuIII and high‐spin FeIII and MnIII 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.

AB - Four 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]⋅CH3OH}n (1) (tren=tris(2‐aminoethyl)amine), {[{Ni(cyclen)}{Ru(acac)2(CN)2}][ClO4]⋅ CH3OH}n (2) (cyclen=1,4,7,10‐tetraazacyclododecane), {[{Fe(salen)}{Ru(acac)2(CN)2}]}n (3) (salen2−=N,N′‐bis(salicylidene)‐o‐ethyldiamine dianion) and [{Mn(5,5′‐Me2salen)}2{Ru(acac)2(CN)2}][Ru(acac)2(CN)2]⋅ 2 CH3OH (4) (5,5′‐Me2salen=N,N′‐bis(5,5′‐dimethylsalicylidene)‐o‐ethylenediimine). Compounds 1 and 2 are 1D, zigzagged NiRu chains that exhibit ferromagnetic coupling between NiII and RuIII ions through cyano bridges with J=+1.92 cm−1, z J′=−1.37 cm−1, g=2.20 for 1 and J=+0.85 cm−1, z J′=−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, z J′=−0.09 cm−1, g=2.08), but antiferromagnetic coupling occurs between FeRu chains, leading to metamagnetic behavior with TN=2.6 K. In compound 4, two MnIII ions are coordinated to trans‐[Ru(acac)2(CN)2]− to form trinuclear Mn2Ru units, which are linked together by π–π stacking and weak Mn⋅⋅⋅O* interactions to form a 1D chain. Compound 4 shows slow magnetic relaxation below 3.0 K with ϕ=0.25, characteristic of superparamagnetic behavior. The MnIII⋅⋅⋅RuIII coupling constant (through cyano bridges) and the MnIII⋅⋅⋅MnIIIcoupling 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 noncovalent 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 RuIII and M (M=NiII, FeIII, and MnIII) ions. To explain the somewhat unexpected ferromagnetic coupling between low‐spin RuIII and high‐spin FeIII and MnIII 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.

KW - Coordination modes

KW - Density functional calculations

KW - Magnetic properties

KW - Moleculebased magnets

KW - Ruthenium

KW - Singlechain magnets

UR - https://www.scopus.com/pages/publications/77949300995

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-77949300995&origin=recordpage

U2 - 10.1002/chem.200902047

DO - 10.1002/chem.200902047

M3 - RGC 21 - Publication in refereed journal

SN - 0947-6539

VL - 16

SP - 3524

EP - 3535

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 11

ER -