Tetranuclear copper(II) and nickel(II) cluster complexes derived by self-assembly from a series of tetradentate diazine ligands: Structural and magnetic studies

Craig J. Matthews; Karen Avery; Zhiqiang Xu; Laurence K. Thompson; Liang Zhao; David O. Miller; Kumar Biradha; Karen Poirier; Michael J. Zaworotko; Claire Wilson; Andrés E. Goeta; Judith A.K. Howard

doi:10.1021/ic990598f

Tetranuclear copper(II) and nickel(II) cluster complexes derived by self-assembly from a series of tetradentate diazine ligands: Structural and magnetic studies

Craig J. Matthews, Karen Avery, Zhiqiang Xu, Laurence K. Thompson, Liang Zhao, David O. Miller, Kumar Biradha, Karen Poirier, Michael J. Zaworotko, Claire Wilson, Andrés E. Goeta, Judith A.K. Howard

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

Abstract

A series of tetranuclear copper(II) and nickel(II) complexes is described, all of which form by a strict self-assembly process involving just a single ligand and the metal salt. The ligands POAP, POAPZ, PZOAP, and 6POAP contain terminal pyridine and pyrazine residues bound to a central flexible diazine subunit (N-N) and contain two potentially bridging groups (alkoxo and diazine). In all cases but one the metals are linked by alkoxo oxygens alone, forming essentially square [M₄(μ₂-O)₄] clusters. A rectangular copper(II) complex [Cu₄(μ₂-N₂)₂-(μ ₂-O)₂] involves a mixture of two alkoxo and two diazine bridges. The square Cu₄O₄ clusters exhibit ferromagnetic coupling between the metal centers, associated with the orthogonal arrangement of magnetic orbitals, while for the Ni₄O₄ clusters the nickel(II) centers are coupled antiferromagnetically. The [Cu₄(μ₂-N₂)₂(μ ₂-O)₂] cluster exhibits strong antiferromagnetic coupling through a trans Cu(N-N)Cu bridging arrangement, typical for systems of this son. X-ray structures are reported for [Cu₄ (POAP-H)₄(H₂O)₂](NO₃) ₄·4H₂O (2), [Cu₄(POAPZ-H)₄(H₂O)](NO₃) ₄·3H₂O (3), [Cu₄(6OAP-H)₄](C1O₄)₄ (4), [Cu₄(PZOAP-H)₄](NO₃)₄·3H ₂O (5), [Ni₄(POAP-H₎4 (H₂O)₄](NO₃)₄·8H₂O (6), and [Ni₄(PZOAP-H)₄(H₂O)₄](ClO ₄)₄·5H₂O (9). 2 crystallized in the monoclinic system, space group C2/c, with a = 20.479(3) Å, b = 14.920(2) Å, c = 19.671(3) Å, β= 90.591(4)°, and Z = 8. 3 crystallized in the monoclinic system, space group P2₁/c, with a = 14.12(1) Å, b = 14.116(3) Å, c = 29.043(4) Å, β= 94.50(3)°, and Z = 4. 4 crystallized in the monoclinic system, space group C2/c, with a = 22.646(4) Å, b = 25.842(5) Å, c = 12.349(5) Å, β= 10.34(2)°, and Z = 4. 5 crystallized in the monoclinic system, space group P2ln, with a = 14.3573(4) Å, b = 10.8910(6) Aring;, c = 20.5360(10) Å, β = 96.975(4)°, and Z = 4. 6 crystallized in the triclinic system, space group P1̄, with a = 12.0509(6) Å, b = 12.7498(6) Å, c = 23.1208 Å, α = 93.1050(10)°, β= 100.1500(10)°, γ = 108.5050(11)°, and Z = 2. 9 crystallized in the orthorhombic system, space group Pbcn, with a = 14.368(4) Å, b = 25.469(7) Å, c = 18.479(5) Å, and Z = 4.

Original language	English
Pages (from-to)	5266-5276
Number of pages	11
Journal	Inorganic Chemistry
Volume	38
Issue number	23
DOIs	https://doi.org/10.1021/ic990598f
Publication status	Published - 1999
Externally published	Yes

Access to Document

10.1021/ic990598f

Cite this

Matthews, C. J., Avery, K., Xu, Z., Thompson, L. K., Zhao, L., Miller, D. O., Biradha, K., Poirier, K., Zaworotko, M. J., Wilson, C., Goeta, A. E., & Howard, J. A. K. (1999). Tetranuclear copper(II) and nickel(II) cluster complexes derived by self-assembly from a series of tetradentate diazine ligands: Structural and magnetic studies. Inorganic Chemistry, 38(23), 5266-5276. https://doi.org/10.1021/ic990598f

@article{abeb803e2c0e495886f2b4cfee9cc124,

title = "Tetranuclear copper(II) and nickel(II) cluster complexes derived by self-assembly from a series of tetradentate diazine ligands: Structural and magnetic studies",

abstract = "A series of tetranuclear copper(II) and nickel(II) complexes is described, all of which form by a strict self-assembly process involving just a single ligand and the metal salt. The ligands POAP, POAPZ, PZOAP, and 6POAP contain terminal pyridine and pyrazine residues bound to a central flexible diazine subunit (N-N) and contain two potentially bridging groups (alkoxo and diazine). In all cases but one the metals are linked by alkoxo oxygens alone, forming essentially square [M4(μ2-O)4] clusters. A rectangular copper(II) complex [Cu4(μ2-N2)2-(μ 2-O)2] involves a mixture of two alkoxo and two diazine bridges. The square Cu4O4 clusters exhibit ferromagnetic coupling between the metal centers, associated with the orthogonal arrangement of magnetic orbitals, while for the Ni4O4 clusters the nickel(II) centers are coupled antiferromagnetically. The [Cu4(μ2-N2)2(μ 2-O)2] cluster exhibits strong antiferromagnetic coupling through a trans Cu(N-N)Cu bridging arrangement, typical for systems of this son. X-ray structures are reported for [Cu4 (POAP-H)4(H2O)2](NO3) 4·4H2O (2), [Cu4(POAPZ-H)4(H2O)](NO3) 4·3H2O (3), [Cu4(6OAP-H)4](C1O4)4 (4), [Cu4(PZOAP-H)4](NO3)4·3H 2O (5), [Ni4(POAP-H)4 (H2O)4](NO3)4·8H2O (6), and [Ni4(PZOAP-H)4(H2O)4](ClO 4)4·5H2O (9). 2 crystallized in the monoclinic system, space group C2/c, with a = 20.479(3) {\AA}, b = 14.920(2) {\AA}, c = 19.671(3) {\AA}, β= 90.591(4)°, and Z = 8. 3 crystallized in the monoclinic system, space group P21/c, with a = 14.12(1) {\AA}, b = 14.116(3) {\AA}, c = 29.043(4) {\AA}, β= 94.50(3)°, and Z = 4. 4 crystallized in the monoclinic system, space group C2/c, with a = 22.646(4) {\AA}, b = 25.842(5) {\AA}, c = 12.349(5) {\AA}, β= 10.34(2)°, and Z = 4. 5 crystallized in the monoclinic system, space group P2ln, with a = 14.3573(4) {\AA}, b = 10.8910(6) Aring;, c = 20.5360(10) {\AA}, β = 96.975(4)°, and Z = 4. 6 crystallized in the triclinic system, space group P{\=1}, with a = 12.0509(6) {\AA}, b = 12.7498(6) {\AA}, c = 23.1208 {\AA}, α = 93.1050(10)°, β= 100.1500(10)°, γ = 108.5050(11)°, and Z = 2. 9 crystallized in the orthorhombic system, space group Pbcn, with a = 14.368(4) {\AA}, b = 25.469(7) {\AA}, c = 18.479(5) {\AA}, and Z = 4.",

author = "Matthews, {Craig J.} and Karen Avery and Zhiqiang Xu and Thompson, {Laurence K.} and Liang Zhao and Miller, {David O.} and Kumar Biradha and Karen Poirier and Zaworotko, {Michael J.} and Claire Wilson and Goeta, {Andr{\'e}s E.} and Howard, {Judith A.K.}",

year = "1999",

doi = "10.1021/ic990598f",

language = "English",

volume = "38",

pages = "5266--5276",

journal = "Inorganic Chemistry",

issn = "0020-1669",

number = "23",

}

Matthews, CJ, Avery, K, Xu, Z, Thompson, LK, Zhao, L, Miller, DO, Biradha, K, Poirier, K, Zaworotko, MJ, Wilson, C, Goeta, AE & Howard, JAK 1999, 'Tetranuclear copper(II) and nickel(II) cluster complexes derived by self-assembly from a series of tetradentate diazine ligands: Structural and magnetic studies', Inorganic Chemistry, vol. 38, no. 23, pp. 5266-5276. https://doi.org/10.1021/ic990598f

TY - JOUR

T1 - Tetranuclear copper(II) and nickel(II) cluster complexes derived by self-assembly from a series of tetradentate diazine ligands

T2 - Structural and magnetic studies

AU - Matthews, Craig J.

AU - Avery, Karen

AU - Xu, Zhiqiang

AU - Thompson, Laurence K.

AU - Zhao, Liang

AU - Miller, David O.

AU - Biradha, Kumar

AU - Poirier, Karen

AU - Zaworotko, Michael J.

AU - Wilson, Claire

AU - Goeta, Andrés E.

AU - Howard, Judith A.K.

PY - 1999

Y1 - 1999

N2 - A series of tetranuclear copper(II) and nickel(II) complexes is described, all of which form by a strict self-assembly process involving just a single ligand and the metal salt. The ligands POAP, POAPZ, PZOAP, and 6POAP contain terminal pyridine and pyrazine residues bound to a central flexible diazine subunit (N-N) and contain two potentially bridging groups (alkoxo and diazine). In all cases but one the metals are linked by alkoxo oxygens alone, forming essentially square [M4(μ2-O)4] clusters. A rectangular copper(II) complex [Cu4(μ2-N2)2-(μ 2-O)2] involves a mixture of two alkoxo and two diazine bridges. The square Cu4O4 clusters exhibit ferromagnetic coupling between the metal centers, associated with the orthogonal arrangement of magnetic orbitals, while for the Ni4O4 clusters the nickel(II) centers are coupled antiferromagnetically. The [Cu4(μ2-N2)2(μ 2-O)2] cluster exhibits strong antiferromagnetic coupling through a trans Cu(N-N)Cu bridging arrangement, typical for systems of this son. X-ray structures are reported for [Cu4 (POAP-H)4(H2O)2](NO3) 4·4H2O (2), [Cu4(POAPZ-H)4(H2O)](NO3) 4·3H2O (3), [Cu4(6OAP-H)4](C1O4)4 (4), [Cu4(PZOAP-H)4](NO3)4·3H 2O (5), [Ni4(POAP-H)4 (H2O)4](NO3)4·8H2O (6), and [Ni4(PZOAP-H)4(H2O)4](ClO 4)4·5H2O (9). 2 crystallized in the monoclinic system, space group C2/c, with a = 20.479(3) Å, b = 14.920(2) Å, c = 19.671(3) Å, β= 90.591(4)°, and Z = 8. 3 crystallized in the monoclinic system, space group P21/c, with a = 14.12(1) Å, b = 14.116(3) Å, c = 29.043(4) Å, β= 94.50(3)°, and Z = 4. 4 crystallized in the monoclinic system, space group C2/c, with a = 22.646(4) Å, b = 25.842(5) Å, c = 12.349(5) Å, β= 10.34(2)°, and Z = 4. 5 crystallized in the monoclinic system, space group P2ln, with a = 14.3573(4) Å, b = 10.8910(6) Aring;, c = 20.5360(10) Å, β = 96.975(4)°, and Z = 4. 6 crystallized in the triclinic system, space group P1̄, with a = 12.0509(6) Å, b = 12.7498(6) Å, c = 23.1208 Å, α = 93.1050(10)°, β= 100.1500(10)°, γ = 108.5050(11)°, and Z = 2. 9 crystallized in the orthorhombic system, space group Pbcn, with a = 14.368(4) Å, b = 25.469(7) Å, c = 18.479(5) Å, and Z = 4.

AB - A series of tetranuclear copper(II) and nickel(II) complexes is described, all of which form by a strict self-assembly process involving just a single ligand and the metal salt. The ligands POAP, POAPZ, PZOAP, and 6POAP contain terminal pyridine and pyrazine residues bound to a central flexible diazine subunit (N-N) and contain two potentially bridging groups (alkoxo and diazine). In all cases but one the metals are linked by alkoxo oxygens alone, forming essentially square [M4(μ2-O)4] clusters. A rectangular copper(II) complex [Cu4(μ2-N2)2-(μ 2-O)2] involves a mixture of two alkoxo and two diazine bridges. The square Cu4O4 clusters exhibit ferromagnetic coupling between the metal centers, associated with the orthogonal arrangement of magnetic orbitals, while for the Ni4O4 clusters the nickel(II) centers are coupled antiferromagnetically. The [Cu4(μ2-N2)2(μ 2-O)2] cluster exhibits strong antiferromagnetic coupling through a trans Cu(N-N)Cu bridging arrangement, typical for systems of this son. X-ray structures are reported for [Cu4 (POAP-H)4(H2O)2](NO3) 4·4H2O (2), [Cu4(POAPZ-H)4(H2O)](NO3) 4·3H2O (3), [Cu4(6OAP-H)4](C1O4)4 (4), [Cu4(PZOAP-H)4](NO3)4·3H 2O (5), [Ni4(POAP-H)4 (H2O)4](NO3)4·8H2O (6), and [Ni4(PZOAP-H)4(H2O)4](ClO 4)4·5H2O (9). 2 crystallized in the monoclinic system, space group C2/c, with a = 20.479(3) Å, b = 14.920(2) Å, c = 19.671(3) Å, β= 90.591(4)°, and Z = 8. 3 crystallized in the monoclinic system, space group P21/c, with a = 14.12(1) Å, b = 14.116(3) Å, c = 29.043(4) Å, β= 94.50(3)°, and Z = 4. 4 crystallized in the monoclinic system, space group C2/c, with a = 22.646(4) Å, b = 25.842(5) Å, c = 12.349(5) Å, β= 10.34(2)°, and Z = 4. 5 crystallized in the monoclinic system, space group P2ln, with a = 14.3573(4) Å, b = 10.8910(6) Aring;, c = 20.5360(10) Å, β = 96.975(4)°, and Z = 4. 6 crystallized in the triclinic system, space group P1̄, with a = 12.0509(6) Å, b = 12.7498(6) Å, c = 23.1208 Å, α = 93.1050(10)°, β= 100.1500(10)°, γ = 108.5050(11)°, and Z = 2. 9 crystallized in the orthorhombic system, space group Pbcn, with a = 14.368(4) Å, b = 25.469(7) Å, c = 18.479(5) Å, and Z = 4.

UR - http://www.scopus.com/inward/record.url?scp=17144379024&partnerID=8YFLogxK

U2 - 10.1021/ic990598f

DO - 10.1021/ic990598f

M3 - Article

AN - SCOPUS:17144379024

SN - 0020-1669

VL - 38

SP - 5266

EP - 5276

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 23

ER -

Tetranuclear copper(II) and nickel(II) cluster complexes derived by self-assembly from a series of tetradentate diazine ligands: Structural and magnetic studies

Abstract

Access to Document

Other files and links

Fingerprint

Cite this