Azido-bridged Cu(II) compounds with asymmetric end-to-end and end-on binding modes: Magnetic assignments using a spin dimer model

Young Sin You; Chang Seop Hong; Kwan Mook Kim

doi:10.1016/j.poly.2004.11.022

Azido-bridged Cu(II) compounds with asymmetric end-to-end and end-on binding modes: Magnetic assignments using a spin dimer model

Young Sin You, Chang Seop Hong, Kwan Mook Kim

Department of Chemistry & Nanoscience

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

41 Scopus citations

Abstract

Dinuclear [Cu(aepi)(N₃)₂]₂ (1) [aepi = 1-(2-aminoethyl)piperidine] and 1D chain [Cu(aepy)(N₃) ₂]_n (2) [aepy = 1-(2-aminoethyl)pyrrolidine] have been prepared and characterized by means of X-ray analysis and magnetic measurements. For 1, the Cu(II) centers are doubly bridged by end-on (EO) azido units in a basal-apical fashion. The molecular structure of 2 features magnetic centers that are linked by μ-1,1,3 azido groups, forming a 1D chain with alternating EO and end-to-end (EE) azido bridging patterns. The magnetic data for the dinuclear complex 1 were fitted with the Bleaney-Bowers equation derived from the Hamiltonian H = -JS₁ • S₂, affording parameters of g = 2.093(1), J = -3.06(1) cm^-1 and zJ′ = -1.32(3) cm ^-1. This indicates that the EO azido group mediates an antiferromagnetic interaction. Complex 2 has two possible magnetic pathways: one is through the EO azido bridge (J_eo) and the other via the EE bridge (J_ee). The alternating chain model with ferromagnetic and antiferromagnetic interactions based on the exchange Hamiltonian H = -∑_iS_2i • S_{2i + 1} + J₂S _2i • S_{2i - 1}] was employed, leading to g = 2.076(2), J₁ = -3.22(5) cm^-1, J₂ = 17.0(5) cm ^-1 and zJ′ = -1.34(6) cm^-1. By taking into account structural parameters of 1 and 2, it is rationally suggested that J₁ and J₂ are ascribed to J_eo andJ_ee, respectively. These assignments are also ascertained by MO calculations using a spin dimer model.

Original language	English
Pages (from-to)	249-256
Number of pages	8
Journal	Polyhedron
Volume	24
Issue number	2
DOIs	https://doi.org/10.1016/j.poly.2004.11.022
State	Published - 27 Jan 2005

Bibliographical note

Funding Information:
This work is financially supported by the CRM-KOSEF. C.S.H. would like to thank an Operation Program on Shared Research Equipment of KBSI and MOST.

Keywords

Azide ligand
Copper(II) compounds
Crystal structures
Magnetic properties

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10.1016/j.poly.2004.11.022

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@article{e1d0f9e3c0da4951b607ce44b2b088e9,

title = "Azido-bridged Cu(II) compounds with asymmetric end-to-end and end-on binding modes: Magnetic assignments using a spin dimer model",

abstract = "Dinuclear [Cu(aepi)(N3)2]2 (1) [aepi = 1-(2-aminoethyl)piperidine] and 1D chain [Cu(aepy)(N3) 2]n (2) [aepy = 1-(2-aminoethyl)pyrrolidine] have been prepared and characterized by means of X-ray analysis and magnetic measurements. For 1, the Cu(II) centers are doubly bridged by end-on (EO) azido units in a basal-apical fashion. The molecular structure of 2 features magnetic centers that are linked by μ-1,1,3 azido groups, forming a 1D chain with alternating EO and end-to-end (EE) azido bridging patterns. The magnetic data for the dinuclear complex 1 were fitted with the Bleaney-Bowers equation derived from the Hamiltonian H = -JS1 • S2, affording parameters of g = 2.093(1), J = -3.06(1) cm-1 and zJ′ = -1.32(3) cm -1. This indicates that the EO azido group mediates an antiferromagnetic interaction. Complex 2 has two possible magnetic pathways: one is through the EO azido bridge (Jeo) and the other via the EE bridge (Jee). The alternating chain model with ferromagnetic and antiferromagnetic interactions based on the exchange Hamiltonian H = -∑iS2i • S2i + 1 + J2S 2i • S2i - 1] was employed, leading to g = 2.076(2), J1 = -3.22(5) cm-1, J2 = 17.0(5) cm -1 and zJ′ = -1.34(6) cm-1. By taking into account structural parameters of 1 and 2, it is rationally suggested that J1 and J2 are ascribed to Jeo andJee, respectively. These assignments are also ascertained by MO calculations using a spin dimer model.",

keywords = "Azide ligand, Copper(II) compounds, Crystal structures, Magnetic properties",

author = "You, {Young Sin} and Hong, {Chang Seop} and Kim, {Kwan Mook}",

note = "Funding Information: This work is financially supported by the CRM-KOSEF. C.S.H. would like to thank an Operation Program on Shared Research Equipment of KBSI and MOST.",

year = "2005",

month = jan,

day = "27",

doi = "10.1016/j.poly.2004.11.022",

language = "English",

volume = "24",

pages = "249--256",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd.",

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TY - JOUR

T1 - Azido-bridged Cu(II) compounds with asymmetric end-to-end and end-on binding modes

T2 - Magnetic assignments using a spin dimer model

AU - You, Young Sin

AU - Hong, Chang Seop

AU - Kim, Kwan Mook

N1 - Funding Information: This work is financially supported by the CRM-KOSEF. C.S.H. would like to thank an Operation Program on Shared Research Equipment of KBSI and MOST.

PY - 2005/1/27

Y1 - 2005/1/27

N2 - Dinuclear [Cu(aepi)(N3)2]2 (1) [aepi = 1-(2-aminoethyl)piperidine] and 1D chain [Cu(aepy)(N3) 2]n (2) [aepy = 1-(2-aminoethyl)pyrrolidine] have been prepared and characterized by means of X-ray analysis and magnetic measurements. For 1, the Cu(II) centers are doubly bridged by end-on (EO) azido units in a basal-apical fashion. The molecular structure of 2 features magnetic centers that are linked by μ-1,1,3 azido groups, forming a 1D chain with alternating EO and end-to-end (EE) azido bridging patterns. The magnetic data for the dinuclear complex 1 were fitted with the Bleaney-Bowers equation derived from the Hamiltonian H = -JS1 • S2, affording parameters of g = 2.093(1), J = -3.06(1) cm-1 and zJ′ = -1.32(3) cm -1. This indicates that the EO azido group mediates an antiferromagnetic interaction. Complex 2 has two possible magnetic pathways: one is through the EO azido bridge (Jeo) and the other via the EE bridge (Jee). The alternating chain model with ferromagnetic and antiferromagnetic interactions based on the exchange Hamiltonian H = -∑iS2i • S2i + 1 + J2S 2i • S2i - 1] was employed, leading to g = 2.076(2), J1 = -3.22(5) cm-1, J2 = 17.0(5) cm -1 and zJ′ = -1.34(6) cm-1. By taking into account structural parameters of 1 and 2, it is rationally suggested that J1 and J2 are ascribed to Jeo andJee, respectively. These assignments are also ascertained by MO calculations using a spin dimer model.

AB - Dinuclear [Cu(aepi)(N3)2]2 (1) [aepi = 1-(2-aminoethyl)piperidine] and 1D chain [Cu(aepy)(N3) 2]n (2) [aepy = 1-(2-aminoethyl)pyrrolidine] have been prepared and characterized by means of X-ray analysis and magnetic measurements. For 1, the Cu(II) centers are doubly bridged by end-on (EO) azido units in a basal-apical fashion. The molecular structure of 2 features magnetic centers that are linked by μ-1,1,3 azido groups, forming a 1D chain with alternating EO and end-to-end (EE) azido bridging patterns. The magnetic data for the dinuclear complex 1 were fitted with the Bleaney-Bowers equation derived from the Hamiltonian H = -JS1 • S2, affording parameters of g = 2.093(1), J = -3.06(1) cm-1 and zJ′ = -1.32(3) cm -1. This indicates that the EO azido group mediates an antiferromagnetic interaction. Complex 2 has two possible magnetic pathways: one is through the EO azido bridge (Jeo) and the other via the EE bridge (Jee). The alternating chain model with ferromagnetic and antiferromagnetic interactions based on the exchange Hamiltonian H = -∑iS2i • S2i + 1 + J2S 2i • S2i - 1] was employed, leading to g = 2.076(2), J1 = -3.22(5) cm-1, J2 = 17.0(5) cm -1 and zJ′ = -1.34(6) cm-1. By taking into account structural parameters of 1 and 2, it is rationally suggested that J1 and J2 are ascribed to Jeo andJee, respectively. These assignments are also ascertained by MO calculations using a spin dimer model.

KW - Azide ligand

KW - Copper(II) compounds

KW - Crystal structures

KW - Magnetic properties

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U2 - 10.1016/j.poly.2004.11.022

DO - 10.1016/j.poly.2004.11.022

M3 - Article

AN - SCOPUS:12344290604

SN - 0277-5387

VL - 24

SP - 249

EP - 256

JO - Polyhedron

JF - Polyhedron

IS - 2

ER -

Azido-bridged Cu(II) compounds with asymmetric end-to-end and end-on binding modes: Magnetic assignments using a spin dimer model

Abstract

Bibliographical note

Keywords

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