Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: Syntheses, crystal structures, and magnetic properties

Zhong Hai Ni; Hui Zhong Kou; Lei Zheng; Yi Hua Zhao; Li Fang Zhang; Ru Ji Wang; Ai Li Cui; Osamu Sato

doi:10.1021/ic050181b

Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)₂]²⁺ building block: Syntheses, crystal structures, and magnetic properties

Zhong Hai Ni, Hui Zhong Kou, Lei Zheng, Yi Hua Zhao, Li Fang Zhang, Ru Ji Wang, Ai Li Cui, Osamu Sato

Research output: Contribution to journal › Article › peer-review

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Abstract

Two new cyano-bridged heterobinuclear complexes, [Mn^II(phen) ₂Cl][Fe^IIIl(bpb)(CN)₂]·0.5CH ₃CH₂OH·1.5H₂O (1) and [Mn ^II(phen)₂Cl][Cr^III(bpb)(CN)₂] ·2H₂O (2) [phen = 1,10-phenanthroline; bpb² = 1,2-bis(pyridine-2-carboxamido)-benzenate], and four novel azido-bridged Mn(II) dimeric complexes, [Mn₂(phen)₄(μ_1,1-N ₃)₂][M^III(bpb)(CN)₂] ₂·H₂O [M = Fe (3), Cr (4), Co (5)] and [Mn ₂(phen)₄(μ_1,3-N₃)(N ₃)₂]BPh₄·0.5H₂O (6), have been synthesized and characterized by single-crystal X-ray diffraction analysis and magnetic studies. Complexes 1 and 2 comprise [Mn(phen)₂Cl] ⁺ and [M(bpb)(CN)₂]^- units connected by one cyano ligand of [M(bpb)(CN)₂]^-. Complexes 3-5 are doubly end-on (EO) azido-bridged Mn(II) binuclear complexes with two [M(bpb)(CN) ₂]^- molecules acting as charge-compensating anions. However, the Mn(II) ions in complex 6 are linked by a single end-to-end (EE) azido bridging ligand with one large free BPh₄^- group as the charge-balancing anion. The magnetic coupling between Mn(II) and Fe(III) or Cr(III) in complexes 1 and 2 was found to be antiferromagnetic with J _MnFe = -2.68(3) cm^-1 and J_MnCr = -4.55(1) cm^-1 on the basis of the Hamiltonian Ĥ = - JŜ_MnŜ_M(M = Fe or Cr). The magnetic interactions between two Mn(II) ions in 3-5 are ferromagnetic in nature with the magnetic coupling constants of 1.15(3), 1.05(2), and 1.27(2) cm^-1 (Ĥ = -JŜ_Mn1Ŝ_Mn2), respectively. The single EE azido-bridged dimeric complex 6 manifests antiferromagnetic interaction with J = -2.29(4) cm^-1 (Ĥ = - JŜ_Mn1Ŝ_Mn2). Magneto-structural correlationship on the EO azido-bridged Mn(II) dimers has been investigated.

Original language	English
Pages (from-to)	4728-4736
Number of pages	9
Journal	Inorganic chemistry
Volume	44
Issue number	13
DOIs	https://doi.org/10.1021/ic050181b
Publication status	Published - Jun 27 2005
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic050181b

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@article{9595de45269e42569f73cd3f456aa53d,

title = "Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: Syntheses, crystal structures, and magnetic properties",

abstract = "Two new cyano-bridged heterobinuclear complexes, [MnII(phen) 2Cl][FeIIIl(bpb)(CN)2]·0.5CH 3CH2OH·1.5H2O (1) and [Mn II(phen)2Cl][CrIII(bpb)(CN)2] ·2H2O (2) [phen = 1,10-phenanthroline; bpb2 = 1,2-bis(pyridine-2-carboxamido)-benzenate], and four novel azido-bridged Mn(II) dimeric complexes, [Mn2(phen)4(μ1,1-N 3)2][MIII(bpb)(CN)2] 2·H2O [M = Fe (3), Cr (4), Co (5)] and [Mn 2(phen)4(μ1,3-N3)(N 3)2]BPh4·0.5H2O (6), have been synthesized and characterized by single-crystal X-ray diffraction analysis and magnetic studies. Complexes 1 and 2 comprise [Mn(phen)2Cl] + and [M(bpb)(CN)2]- units connected by one cyano ligand of [M(bpb)(CN)2]-. Complexes 3-5 are doubly end-on (EO) azido-bridged Mn(II) binuclear complexes with two [M(bpb)(CN) 2]- molecules acting as charge-compensating anions. However, the Mn(II) ions in complex 6 are linked by a single end-to-end (EE) azido bridging ligand with one large free BPh4- group as the charge-balancing anion. The magnetic coupling between Mn(II) and Fe(III) or Cr(III) in complexes 1 and 2 was found to be antiferromagnetic with J MnFe = -2.68(3) cm-1 and JMnCr = -4.55(1) cm-1 on the basis of the Hamiltonian Ĥ = - JŜMnŜM(M = Fe or Cr). The magnetic interactions between two Mn(II) ions in 3-5 are ferromagnetic in nature with the magnetic coupling constants of 1.15(3), 1.05(2), and 1.27(2) cm-1 (Ĥ = -JŜMn1ŜMn2), respectively. The single EE azido-bridged dimeric complex 6 manifests antiferromagnetic interaction with J = -2.29(4) cm-1 (Ĥ = - JŜMn1ŜMn2). Magneto-structural correlationship on the EO azido-bridged Mn(II) dimers has been investigated.",

author = "Ni, {Zhong Hai} and Kou, {Hui Zhong} and Lei Zheng and Zhao, {Yi Hua} and Zhang, {Li Fang} and Wang, {Ru Ji} and Cui, {Ai Li} and Osamu Sato",

year = "2005",

month = jun,

day = "27",

doi = "10.1021/ic050181b",

language = "English",

volume = "44",

pages = "4728--4736",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "13",

}

TY - JOUR

T1 - Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block

T2 - Syntheses, crystal structures, and magnetic properties

AU - Ni, Zhong Hai

AU - Kou, Hui Zhong

AU - Zheng, Lei

AU - Zhao, Yi Hua

AU - Zhang, Li Fang

AU - Wang, Ru Ji

AU - Cui, Ai Li

AU - Sato, Osamu

PY - 2005/6/27

Y1 - 2005/6/27

N2 - Two new cyano-bridged heterobinuclear complexes, [MnII(phen) 2Cl][FeIIIl(bpb)(CN)2]·0.5CH 3CH2OH·1.5H2O (1) and [Mn II(phen)2Cl][CrIII(bpb)(CN)2] ·2H2O (2) [phen = 1,10-phenanthroline; bpb2 = 1,2-bis(pyridine-2-carboxamido)-benzenate], and four novel azido-bridged Mn(II) dimeric complexes, [Mn2(phen)4(μ1,1-N 3)2][MIII(bpb)(CN)2] 2·H2O [M = Fe (3), Cr (4), Co (5)] and [Mn 2(phen)4(μ1,3-N3)(N 3)2]BPh4·0.5H2O (6), have been synthesized and characterized by single-crystal X-ray diffraction analysis and magnetic studies. Complexes 1 and 2 comprise [Mn(phen)2Cl] + and [M(bpb)(CN)2]- units connected by one cyano ligand of [M(bpb)(CN)2]-. Complexes 3-5 are doubly end-on (EO) azido-bridged Mn(II) binuclear complexes with two [M(bpb)(CN) 2]- molecules acting as charge-compensating anions. However, the Mn(II) ions in complex 6 are linked by a single end-to-end (EE) azido bridging ligand with one large free BPh4- group as the charge-balancing anion. The magnetic coupling between Mn(II) and Fe(III) or Cr(III) in complexes 1 and 2 was found to be antiferromagnetic with J MnFe = -2.68(3) cm-1 and JMnCr = -4.55(1) cm-1 on the basis of the Hamiltonian Ĥ = - JŜMnŜM(M = Fe or Cr). The magnetic interactions between two Mn(II) ions in 3-5 are ferromagnetic in nature with the magnetic coupling constants of 1.15(3), 1.05(2), and 1.27(2) cm-1 (Ĥ = -JŜMn1ŜMn2), respectively. The single EE azido-bridged dimeric complex 6 manifests antiferromagnetic interaction with J = -2.29(4) cm-1 (Ĥ = - JŜMn1ŜMn2). Magneto-structural correlationship on the EO azido-bridged Mn(II) dimers has been investigated.

AB - Two new cyano-bridged heterobinuclear complexes, [MnII(phen) 2Cl][FeIIIl(bpb)(CN)2]·0.5CH 3CH2OH·1.5H2O (1) and [Mn II(phen)2Cl][CrIII(bpb)(CN)2] ·2H2O (2) [phen = 1,10-phenanthroline; bpb2 = 1,2-bis(pyridine-2-carboxamido)-benzenate], and four novel azido-bridged Mn(II) dimeric complexes, [Mn2(phen)4(μ1,1-N 3)2][MIII(bpb)(CN)2] 2·H2O [M = Fe (3), Cr (4), Co (5)] and [Mn 2(phen)4(μ1,3-N3)(N 3)2]BPh4·0.5H2O (6), have been synthesized and characterized by single-crystal X-ray diffraction analysis and magnetic studies. Complexes 1 and 2 comprise [Mn(phen)2Cl] + and [M(bpb)(CN)2]- units connected by one cyano ligand of [M(bpb)(CN)2]-. Complexes 3-5 are doubly end-on (EO) azido-bridged Mn(II) binuclear complexes with two [M(bpb)(CN) 2]- molecules acting as charge-compensating anions. However, the Mn(II) ions in complex 6 are linked by a single end-to-end (EE) azido bridging ligand with one large free BPh4- group as the charge-balancing anion. The magnetic coupling between Mn(II) and Fe(III) or Cr(III) in complexes 1 and 2 was found to be antiferromagnetic with J MnFe = -2.68(3) cm-1 and JMnCr = -4.55(1) cm-1 on the basis of the Hamiltonian Ĥ = - JŜMnŜM(M = Fe or Cr). The magnetic interactions between two Mn(II) ions in 3-5 are ferromagnetic in nature with the magnetic coupling constants of 1.15(3), 1.05(2), and 1.27(2) cm-1 (Ĥ = -JŜMn1ŜMn2), respectively. The single EE azido-bridged dimeric complex 6 manifests antiferromagnetic interaction with J = -2.29(4) cm-1 (Ĥ = - JŜMn1ŜMn2). Magneto-structural correlationship on the EO azido-bridged Mn(II) dimers has been investigated.

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U2 - 10.1021/ic050181b

DO - 10.1021/ic050181b

M3 - Article

C2 - 15962981

AN - SCOPUS:22644445666

SN - 0020-1669

VL - 44

SP - 4728

EP - 4736

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 13

ER -

Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)₂]²⁺ building block: Syntheses, crystal structures, and magnetic properties

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