Imidazolate-bridged copper(II) complexes with infinite zigzag-chain and tetranuclear structures formed by deprotonation and self-assembly

Naohide Matsumoto, Takeshi Nozaki, Hiroyuki Ushio, Ken Ichiro Motoda, Masaaki Ohba, Genjin Mago, Hisashi Ökawa

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Abstract

A method of molecular design of self-assembling metal complexes has been established. The copper(II) complex with a quadridentate ligand [Cu(HL2)]ClO4 undergoes deprotonation of the imidazole proton under basic conditions to give an imidazolate-bridged polymeric compound [(CuL2)∞], where H2L2 = N-3-ethoxysalicylidene-N′-imidazol-4-ylmethylenecyclohexane-1,2-diamine. The latter compound crystallizes in the monoclinic space group P21/a with a = 15.515(5), b = 9.338(5), c = 12.660(2) Å, β = 95.33(2)°, and Z = 4, R = 0.078 for 1721 reflections. It has an infinite zigzag-chain structure and the variable-temperature magnetic data are well reproduced using the Ising model based on H = -2∑JijSiSj with a J value of -1.8 cm-1. The complex [Cu(HL3)Cl]ClO4 with a tridentate ligand gives an imidazolate-bridged tetranuclear complex [(CuL3)4][Clo4]4 on deprotonation at the imidazole nitrogen, where HL3 = N-imidazol-4-ylmethylene-N′,N′-dimethylpropane-1,3-diamine. The latter compound crystallizes in the triclinic space group P1 with a = 15.216(6), b = 15.592(5), c = 15.102(5) Å, α = 104.98(3)°, β = 108.44(3)°, γ = 61.12(2)°, Z = 2, and R = 0.096 for 6931 reflections. The structure consists of a cyclic tetranuclear molecule in which each imidazolate nitrogen atom co-ordinates axially to the copper(II) ion of the adjacent unit. Variable-temperature magnetic data are well reproduced using the Heisenberg model based on H = -2J(S1·S2 + S2·S3 + S3·S4 + S4·S1) with J = -60.0 cm-1.

Original languageEnglish
Pages (from-to)2157-2162
Number of pages6
JournalJournal of the Chemical Society, Dalton Transactions
Issue number14
DOIs
Publication statusPublished - 1993

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Deprotonation
Self assembly
Copper
Diamines
Nitrogen
Ligands
Ising model
Coordination Complexes
Protons
Ions
Atoms
Temperature
Molecules
perchlorate
imidazole

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Imidazolate-bridged copper(II) complexes with infinite zigzag-chain and tetranuclear structures formed by deprotonation and self-assembly. / Matsumoto, Naohide; Nozaki, Takeshi; Ushio, Hiroyuki; Motoda, Ken Ichiro; Ohba, Masaaki; Mago, Genjin; Ökawa, Hisashi.

In: Journal of the Chemical Society, Dalton Transactions, No. 14, 1993, p. 2157-2162.

Research output: Contribution to journalArticle

Matsumoto, Naohide ; Nozaki, Takeshi ; Ushio, Hiroyuki ; Motoda, Ken Ichiro ; Ohba, Masaaki ; Mago, Genjin ; Ökawa, Hisashi. / Imidazolate-bridged copper(II) complexes with infinite zigzag-chain and tetranuclear structures formed by deprotonation and self-assembly. In: Journal of the Chemical Society, Dalton Transactions. 1993 ; No. 14. pp. 2157-2162.
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abstract = "A method of molecular design of self-assembling metal complexes has been established. The copper(II) complex with a quadridentate ligand [Cu(HL2)]ClO4 undergoes deprotonation of the imidazole proton under basic conditions to give an imidazolate-bridged polymeric compound [(CuL2)∞], where H2L2 = N-3-ethoxysalicylidene-N′-imidazol-4-ylmethylenecyclohexane-1,2-diamine. The latter compound crystallizes in the monoclinic space group P21/a with a = 15.515(5), b = 9.338(5), c = 12.660(2) {\AA}, β = 95.33(2)°, and Z = 4, R = 0.078 for 1721 reflections. It has an infinite zigzag-chain structure and the variable-temperature magnetic data are well reproduced using the Ising model based on H = -2∑JijSiSj with a J value of -1.8 cm-1. The complex [Cu(HL3)Cl]ClO4 with a tridentate ligand gives an imidazolate-bridged tetranuclear complex [(CuL3)4][Clo4]4 on deprotonation at the imidazole nitrogen, where HL3 = N-imidazol-4-ylmethylene-N′,N′-dimethylpropane-1,3-diamine. The latter compound crystallizes in the triclinic space group P1 with a = 15.216(6), b = 15.592(5), c = 15.102(5) {\AA}, α = 104.98(3)°, β = 108.44(3)°, γ = 61.12(2)°, Z = 2, and R = 0.096 for 6931 reflections. The structure consists of a cyclic tetranuclear molecule in which each imidazolate nitrogen atom co-ordinates axially to the copper(II) ion of the adjacent unit. Variable-temperature magnetic data are well reproduced using the Heisenberg model based on H = -2J(S1·S2 + S2·S3 + S3·S4 + S4·S1) with J = -60.0 cm-1.",
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T1 - Imidazolate-bridged copper(II) complexes with infinite zigzag-chain and tetranuclear structures formed by deprotonation and self-assembly

AU - Matsumoto, Naohide

AU - Nozaki, Takeshi

AU - Ushio, Hiroyuki

AU - Motoda, Ken Ichiro

AU - Ohba, Masaaki

AU - Mago, Genjin

AU - Ökawa, Hisashi

PY - 1993

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N2 - A method of molecular design of self-assembling metal complexes has been established. The copper(II) complex with a quadridentate ligand [Cu(HL2)]ClO4 undergoes deprotonation of the imidazole proton under basic conditions to give an imidazolate-bridged polymeric compound [(CuL2)∞], where H2L2 = N-3-ethoxysalicylidene-N′-imidazol-4-ylmethylenecyclohexane-1,2-diamine. The latter compound crystallizes in the monoclinic space group P21/a with a = 15.515(5), b = 9.338(5), c = 12.660(2) Å, β = 95.33(2)°, and Z = 4, R = 0.078 for 1721 reflections. It has an infinite zigzag-chain structure and the variable-temperature magnetic data are well reproduced using the Ising model based on H = -2∑JijSiSj with a J value of -1.8 cm-1. The complex [Cu(HL3)Cl]ClO4 with a tridentate ligand gives an imidazolate-bridged tetranuclear complex [(CuL3)4][Clo4]4 on deprotonation at the imidazole nitrogen, where HL3 = N-imidazol-4-ylmethylene-N′,N′-dimethylpropane-1,3-diamine. The latter compound crystallizes in the triclinic space group P1 with a = 15.216(6), b = 15.592(5), c = 15.102(5) Å, α = 104.98(3)°, β = 108.44(3)°, γ = 61.12(2)°, Z = 2, and R = 0.096 for 6931 reflections. The structure consists of a cyclic tetranuclear molecule in which each imidazolate nitrogen atom co-ordinates axially to the copper(II) ion of the adjacent unit. Variable-temperature magnetic data are well reproduced using the Heisenberg model based on H = -2J(S1·S2 + S2·S3 + S3·S4 + S4·S1) with J = -60.0 cm-1.

AB - A method of molecular design of self-assembling metal complexes has been established. The copper(II) complex with a quadridentate ligand [Cu(HL2)]ClO4 undergoes deprotonation of the imidazole proton under basic conditions to give an imidazolate-bridged polymeric compound [(CuL2)∞], where H2L2 = N-3-ethoxysalicylidene-N′-imidazol-4-ylmethylenecyclohexane-1,2-diamine. The latter compound crystallizes in the monoclinic space group P21/a with a = 15.515(5), b = 9.338(5), c = 12.660(2) Å, β = 95.33(2)°, and Z = 4, R = 0.078 for 1721 reflections. It has an infinite zigzag-chain structure and the variable-temperature magnetic data are well reproduced using the Ising model based on H = -2∑JijSiSj with a J value of -1.8 cm-1. The complex [Cu(HL3)Cl]ClO4 with a tridentate ligand gives an imidazolate-bridged tetranuclear complex [(CuL3)4][Clo4]4 on deprotonation at the imidazole nitrogen, where HL3 = N-imidazol-4-ylmethylene-N′,N′-dimethylpropane-1,3-diamine. The latter compound crystallizes in the triclinic space group P1 with a = 15.216(6), b = 15.592(5), c = 15.102(5) Å, α = 104.98(3)°, β = 108.44(3)°, γ = 61.12(2)°, Z = 2, and R = 0.096 for 6931 reflections. The structure consists of a cyclic tetranuclear molecule in which each imidazolate nitrogen atom co-ordinates axially to the copper(II) ion of the adjacent unit. Variable-temperature magnetic data are well reproduced using the Heisenberg model based on H = -2J(S1·S2 + S2·S3 + S3·S4 + S4·S1) with J = -60.0 cm-1.

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