Azide bridged dicopper(II), dicobalt(II) complexes and a rare double μ-chloride bridged ferromagnetic dicobalt(II) complex of a pyrazolyl-pyrimidine ligand: Synthesis, crystal structures, magnetic and DFT studies

Atanu Jana; Saugata Konar; Kinsuk Das; Sangita Ray; James A. Golen; Arnold L. Rheingold; Luca M. Carrella; Eva Rentschler; Tapan Kumar Mondal; Susanta Kumar Kar

doi:10.1016/j.poly.2012.03.010

Azide bridged dicopper(II), dicobalt(II) complexes and a rare double μ-chloride bridged ferromagnetic dicobalt(II) complex of a pyrazolyl-pyrimidine ligand: Synthesis, crystal structures, magnetic and DFT studies

Atanu Jana
, Saugata Konar
, Kinsuk Das
, Sangita Ray
, James A. Golen
, Arnold L. Rheingold
, Luca M. Carrella
, Eva Rentschler
, Tapan Kumar Mondal
, Susanta Kumar Kar

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

30 Scopus citations

Abstract

Two new dinuclear copper(II) complexes [Cu ₂(PymPz) ₂(N ₃) ₂Cl ₂] (1), [Cu ₂(PymPz) ₂(N ₃) ₄] (2) and two new dinuclear cobalt(II) complexes [Co ₂(PymPz) ₂Cl ₄] (3), [Co ₂(PymPz) ₂(N ₃) ₄] (4) [PymPz = 2-(3,5-dimethyl-1H-pyrazol-1-yl)-4,6-dimethylpyrimidine] have been synthesized and characterized crystallographically and spectroscopically. In each of the complexes 1, 2 and 4 the two adjacent metal centers are bridged by a pair of μ-1,1 azide groups whereas in 3 the metal centers are bridged by a pair of chloride ions. In the complexes, all the metal centers are pentacoordinated. In 1 and 2 the copper(II) centers have distorted square pyramidal geometry (τ = 0.18 for 1 and 0.091 for 2) but in 3 and 4 cobalt(II) centers have distorted trigonal bipyramidal geometry (τ = 0.619 for 3 and 0.557 for 4). Complexes 1 and 2 show antiferromagnetic interaction (J = -7.09 cm ^-1 for 1 and J = -17.00 cm ^-1 for 2) whereas 3 and 4 show ferromagnetic interaction (J = 7.44 cm ^-1 for 3 and J = 10.45 cm ^-1 for 4). Complex 3 displays an unprecedented ferromagnetic interaction over double μ-chloro bridges in the observed angle range (94.87°). The exchange pathways parameters for all the complexes have also been evaluated from density functional theoretical calculations to corroborate the bridging signatures with experimental findings.

Original language	English
Pages (from-to)	258-266
Number of pages	9
Journal	Polyhedron
Volume	38
Issue number	1
DOIs	https://doi.org/10.1016/j.poly.2012.03.010
State	Published - 11 May 2012

Keywords

Coordination
Crystal
DFT
Magnetism

Access to Document

10.1016/j.poly.2012.03.010

Fingerprint

Dive into the research topics of 'Azide bridged dicopper(II), dicobalt(II) complexes and a rare double μ-chloride bridged ferromagnetic dicobalt(II) complex of a pyrazolyl-pyrimidine ligand: Synthesis, crystal structures, magnetic and DFT studies'. Together they form a unique fingerprint.

Cite this

Jana, A., Konar, S., Das, K., Ray, S., Golen, J. A., Rheingold, A. L., Carrella, L. M., Rentschler, E., Mondal, T. K., & Kar, S. K. (2012). Azide bridged dicopper(II), dicobalt(II) complexes and a rare double μ-chloride bridged ferromagnetic dicobalt(II) complex of a pyrazolyl-pyrimidine ligand: Synthesis, crystal structures, magnetic and DFT studies. Polyhedron, 38(1), 258-266. https://doi.org/10.1016/j.poly.2012.03.010

@article{47b00b8df96b41728a77f859ddb4fa1b,

title = "Azide bridged dicopper(II), dicobalt(II) complexes and a rare double μ-chloride bridged ferromagnetic dicobalt(II) complex of a pyrazolyl-pyrimidine ligand: Synthesis, crystal structures, magnetic and DFT studies",

abstract = "Two new dinuclear copper(II) complexes [Cu 2(PymPz) 2(N 3) 2Cl 2] (1), [Cu 2(PymPz) 2(N 3) 4] (2) and two new dinuclear cobalt(II) complexes [Co 2(PymPz) 2Cl 4] (3), [Co 2(PymPz) 2(N 3) 4] (4) [PymPz = 2-(3,5-dimethyl-1H-pyrazol-1-yl)-4,6-dimethylpyrimidine] have been synthesized and characterized crystallographically and spectroscopically. In each of the complexes 1, 2 and 4 the two adjacent metal centers are bridged by a pair of μ-1,1 azide groups whereas in 3 the metal centers are bridged by a pair of chloride ions. In the complexes, all the metal centers are pentacoordinated. In 1 and 2 the copper(II) centers have distorted square pyramidal geometry (τ = 0.18 for 1 and 0.091 for 2) but in 3 and 4 cobalt(II) centers have distorted trigonal bipyramidal geometry (τ = 0.619 for 3 and 0.557 for 4). Complexes 1 and 2 show antiferromagnetic interaction (J = -7.09 cm -1 for 1 and J = -17.00 cm -1 for 2) whereas 3 and 4 show ferromagnetic interaction (J = 7.44 cm -1 for 3 and J = 10.45 cm -1 for 4). Complex 3 displays an unprecedented ferromagnetic interaction over double μ-chloro bridges in the observed angle range (94.87°). The exchange pathways parameters for all the complexes have also been evaluated from density functional theoretical calculations to corroborate the bridging signatures with experimental findings.",

keywords = "Coordination, Crystal, DFT, Magnetism",

author = "Atanu Jana and Saugata Konar and Kinsuk Das and Sangita Ray and Golen, \{James A.\} and Rheingold, \{Arnold L.\} and Carrella, \{Luca M.\} and Eva Rentschler and Mondal, \{Tapan Kumar\} and Kar, \{Susanta Kumar\}",

year = "2012",

month = may,

day = "11",

doi = "10.1016/j.poly.2012.03.010",

language = "English",

volume = "38",

pages = "258--266",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd",

number = "1",

}

Jana, A, Konar, S, Das, K, Ray, S, Golen, JA, Rheingold, AL, Carrella, LM, Rentschler, E, Mondal, TK & Kar, SK 2012, 'Azide bridged dicopper(II), dicobalt(II) complexes and a rare double μ-chloride bridged ferromagnetic dicobalt(II) complex of a pyrazolyl-pyrimidine ligand: Synthesis, crystal structures, magnetic and DFT studies', Polyhedron, vol. 38, no. 1, pp. 258-266. https://doi.org/10.1016/j.poly.2012.03.010

Azide bridged dicopper(II), dicobalt(II) complexes and a rare double μ-chloride bridged ferromagnetic dicobalt(II) complex of a pyrazolyl-pyrimidine ligand: Synthesis, crystal structures, magnetic and DFT studies. / Jana, Atanu; Konar, Saugata; Das, Kinsuk et al.
In: Polyhedron, Vol. 38, No. 1, 11.05.2012, p. 258-266.

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

TY - JOUR

T1 - Azide bridged dicopper(II), dicobalt(II) complexes and a rare double μ-chloride bridged ferromagnetic dicobalt(II) complex of a pyrazolyl-pyrimidine ligand

T2 - Synthesis, crystal structures, magnetic and DFT studies

AU - Jana, Atanu

AU - Konar, Saugata

AU - Das, Kinsuk

AU - Ray, Sangita

AU - Golen, James A.

AU - Rheingold, Arnold L.

AU - Carrella, Luca M.

AU - Rentschler, Eva

AU - Mondal, Tapan Kumar

AU - Kar, Susanta Kumar

PY - 2012/5/11

Y1 - 2012/5/11

N2 - Two new dinuclear copper(II) complexes [Cu 2(PymPz) 2(N 3) 2Cl 2] (1), [Cu 2(PymPz) 2(N 3) 4] (2) and two new dinuclear cobalt(II) complexes [Co 2(PymPz) 2Cl 4] (3), [Co 2(PymPz) 2(N 3) 4] (4) [PymPz = 2-(3,5-dimethyl-1H-pyrazol-1-yl)-4,6-dimethylpyrimidine] have been synthesized and characterized crystallographically and spectroscopically. In each of the complexes 1, 2 and 4 the two adjacent metal centers are bridged by a pair of μ-1,1 azide groups whereas in 3 the metal centers are bridged by a pair of chloride ions. In the complexes, all the metal centers are pentacoordinated. In 1 and 2 the copper(II) centers have distorted square pyramidal geometry (τ = 0.18 for 1 and 0.091 for 2) but in 3 and 4 cobalt(II) centers have distorted trigonal bipyramidal geometry (τ = 0.619 for 3 and 0.557 for 4). Complexes 1 and 2 show antiferromagnetic interaction (J = -7.09 cm -1 for 1 and J = -17.00 cm -1 for 2) whereas 3 and 4 show ferromagnetic interaction (J = 7.44 cm -1 for 3 and J = 10.45 cm -1 for 4). Complex 3 displays an unprecedented ferromagnetic interaction over double μ-chloro bridges in the observed angle range (94.87°). The exchange pathways parameters for all the complexes have also been evaluated from density functional theoretical calculations to corroborate the bridging signatures with experimental findings.

AB - Two new dinuclear copper(II) complexes [Cu 2(PymPz) 2(N 3) 2Cl 2] (1), [Cu 2(PymPz) 2(N 3) 4] (2) and two new dinuclear cobalt(II) complexes [Co 2(PymPz) 2Cl 4] (3), [Co 2(PymPz) 2(N 3) 4] (4) [PymPz = 2-(3,5-dimethyl-1H-pyrazol-1-yl)-4,6-dimethylpyrimidine] have been synthesized and characterized crystallographically and spectroscopically. In each of the complexes 1, 2 and 4 the two adjacent metal centers are bridged by a pair of μ-1,1 azide groups whereas in 3 the metal centers are bridged by a pair of chloride ions. In the complexes, all the metal centers are pentacoordinated. In 1 and 2 the copper(II) centers have distorted square pyramidal geometry (τ = 0.18 for 1 and 0.091 for 2) but in 3 and 4 cobalt(II) centers have distorted trigonal bipyramidal geometry (τ = 0.619 for 3 and 0.557 for 4). Complexes 1 and 2 show antiferromagnetic interaction (J = -7.09 cm -1 for 1 and J = -17.00 cm -1 for 2) whereas 3 and 4 show ferromagnetic interaction (J = 7.44 cm -1 for 3 and J = 10.45 cm -1 for 4). Complex 3 displays an unprecedented ferromagnetic interaction over double μ-chloro bridges in the observed angle range (94.87°). The exchange pathways parameters for all the complexes have also been evaluated from density functional theoretical calculations to corroborate the bridging signatures with experimental findings.

KW - Coordination

KW - Crystal

KW - DFT

KW - Magnetism

UR - https://www.scopus.com/pages/publications/84860142802

U2 - 10.1016/j.poly.2012.03.010

DO - 10.1016/j.poly.2012.03.010

M3 - Article

AN - SCOPUS:84860142802

SN - 0277-5387

VL - 38

SP - 258

EP - 266

JO - Polyhedron

JF - Polyhedron

IS - 1

ER -

Azide bridged dicopper(II), dicobalt(II) complexes and a rare double μ-chloride bridged ferromagnetic dicobalt(II) complex of a pyrazolyl-pyrimidine ligand: Synthesis, crystal structures, magnetic and DFT studies

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this