New ferromagnetic dinuclear triply-bridged copper(II) compounds containing carboxylato bridges: Synthesis, X-ray structure and magnetic properties

Sujittra Youngme; Jaturong Phatchimkun; Nanthawat Wannarit; Narongsak Chaichit; Siwaporn Meejoo; Gerard A. van Albada; Jan Reedijk

doi:10.1016/j.poly.2007.09.009

New ferromagnetic dinuclear triply-bridged copper(II) compounds containing carboxylato bridges: Synthesis, X-ray structure and magnetic properties

Sujittra Youngme
, Jaturong Phatchimkun
, Nanthawat Wannarit
, Narongsak Chaichit
, Siwaporn Meejoo
, Gerard A. van Albada
, Jan Reedijk

Faculty of Science, Khon Kaen University
Thammasat University
Mahidol University
Leiden University

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

49 Citations (Scopus)

Abstract

The new triply-bridged dinuclear copper(II) complexes, [Cu₂(μ-O₂CH)(μ-OH)₂(dpyam)₂](ClO₄) · H₂O (1), [Cu₂(μ-O₂CCH₃)(μ-OH)(μ-OH₂)(dpyam)₂](S₂O₈) (2), [Cu₂(μ-O₂CCH₃)(μ-OH)(μ-OH₂)(bpy)₂](NO₃)₂ (3), [Cu₂(μ-O₂CCH₃)(μ-OH)(μ-OH₂)(phen)₂](BF₄)₂ · 0.5H₂O (4), [Cu₂(μ-O₂CCH₂CH₃)(μ-OH)(μ-OH₂)(phen)₂](NO₃)₂ (5) and [Cu₂(μ-O₂CCH₃)(μ-OH)(μ-Cl)(bpy)₂]Cl · 8.5H₂O (6) (dpyam = di-2-pyridylamine, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized and characterized crystallographically and also their spectroscopic and magnetic properties have been studied. A structural classification of this type of dimers, based on the data obtained from X-ray diffraction analysis in the present work and those reported in the literature has been performed. In these complexes, the local geometry around the copper centre is generally a distorted square pyramid and distorted trigonal bipyramid with different degrees of distortion. The global geometry of the dinuclear complexes can be described in terms of the relative arrangement of the two five-coordinate environments, giving rise to different classes (A-F) of complexes. The most logical explanations have been provided for each class describing different magnetic interactions. Practically, there is a clear correlation between structural data and J values of the class B complexes. Extended Hückel calculations were performed for the present complexes 1-6, as well as for some other class B complexes, showing the different molecular orbitals involved in their corresponding frontier orbitals, together with their energy. The results are found to be useful for the proper interpretation and correlation of the magnetic data and the dinuclear structure of the present complexes.

Original language	English
Pages (from-to)	304-318
Number of pages	15
Journal	Polyhedron
Volume	27
Issue number	1
DOIs	https://doi.org/10.1016/j.poly.2007.09.009
Publication status	Published - 20 Jan 2008
Externally published	Yes

Keywords

Copper(II) complexes
Crystal structure
EPR
Magnetism
Triply-bridged

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10.1016/j.poly.2007.09.009

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@article{71aa472a0c3845a4bd772c8a7f5ce7f9,

title = "New ferromagnetic dinuclear triply-bridged copper(II) compounds containing carboxylato bridges: Synthesis, X-ray structure and magnetic properties",

abstract = "The new triply-bridged dinuclear copper(II) complexes, [Cu2(μ-O2CH)(μ-OH)2(dpyam)2](ClO4) · H2O (1), [Cu2(μ-O2CCH3)(μ-OH)(μ-OH2)(dpyam)2](S2O8) (2), [Cu2(μ-O2CCH3)(μ-OH)(μ-OH2)(bpy)2](NO3)2 (3), [Cu2(μ-O2CCH3)(μ-OH)(μ-OH2)(phen)2](BF4)2 · 0.5H2O (4), [Cu2(μ-O2CCH2CH3)(μ-OH)(μ-OH2)(phen)2](NO3)2 (5) and [Cu2(μ-O2CCH3)(μ-OH)(μ-Cl)(bpy)2]Cl · 8.5H2O (6) (dpyam = di-2-pyridylamine, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized and characterized crystallographically and also their spectroscopic and magnetic properties have been studied. A structural classification of this type of dimers, based on the data obtained from X-ray diffraction analysis in the present work and those reported in the literature has been performed. In these complexes, the local geometry around the copper centre is generally a distorted square pyramid and distorted trigonal bipyramid with different degrees of distortion. The global geometry of the dinuclear complexes can be described in terms of the relative arrangement of the two five-coordinate environments, giving rise to different classes (A-F) of complexes. The most logical explanations have been provided for each class describing different magnetic interactions. Practically, there is a clear correlation between structural data and J values of the class B complexes. Extended H{\"u}ckel calculations were performed for the present complexes 1-6, as well as for some other class B complexes, showing the different molecular orbitals involved in their corresponding frontier orbitals, together with their energy. The results are found to be useful for the proper interpretation and correlation of the magnetic data and the dinuclear structure of the present complexes.",

keywords = "Copper(II) complexes, Crystal structure, EPR, Magnetism, Triply-bridged",

author = "Sujittra Youngme and Jaturong Phatchimkun and Nanthawat Wannarit and Narongsak Chaichit and Siwaporn Meejoo and \{van Albada\}, \{Gerard A.\} and Jan Reedijk",

year = "2008",

month = jan,

day = "20",

doi = "10.1016/j.poly.2007.09.009",

language = "English",

volume = "27",

pages = "304--318",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd.",

number = "1",

}

TY - JOUR

T1 - New ferromagnetic dinuclear triply-bridged copper(II) compounds containing carboxylato bridges

T2 - Synthesis, X-ray structure and magnetic properties

AU - Youngme, Sujittra

AU - Phatchimkun, Jaturong

AU - Wannarit, Nanthawat

AU - Chaichit, Narongsak

AU - Meejoo, Siwaporn

AU - van Albada, Gerard A.

AU - Reedijk, Jan

PY - 2008/1/20

Y1 - 2008/1/20

N2 - The new triply-bridged dinuclear copper(II) complexes, [Cu2(μ-O2CH)(μ-OH)2(dpyam)2](ClO4) · H2O (1), [Cu2(μ-O2CCH3)(μ-OH)(μ-OH2)(dpyam)2](S2O8) (2), [Cu2(μ-O2CCH3)(μ-OH)(μ-OH2)(bpy)2](NO3)2 (3), [Cu2(μ-O2CCH3)(μ-OH)(μ-OH2)(phen)2](BF4)2 · 0.5H2O (4), [Cu2(μ-O2CCH2CH3)(μ-OH)(μ-OH2)(phen)2](NO3)2 (5) and [Cu2(μ-O2CCH3)(μ-OH)(μ-Cl)(bpy)2]Cl · 8.5H2O (6) (dpyam = di-2-pyridylamine, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized and characterized crystallographically and also their spectroscopic and magnetic properties have been studied. A structural classification of this type of dimers, based on the data obtained from X-ray diffraction analysis in the present work and those reported in the literature has been performed. In these complexes, the local geometry around the copper centre is generally a distorted square pyramid and distorted trigonal bipyramid with different degrees of distortion. The global geometry of the dinuclear complexes can be described in terms of the relative arrangement of the two five-coordinate environments, giving rise to different classes (A-F) of complexes. The most logical explanations have been provided for each class describing different magnetic interactions. Practically, there is a clear correlation between structural data and J values of the class B complexes. Extended Hückel calculations were performed for the present complexes 1-6, as well as for some other class B complexes, showing the different molecular orbitals involved in their corresponding frontier orbitals, together with their energy. The results are found to be useful for the proper interpretation and correlation of the magnetic data and the dinuclear structure of the present complexes.

AB - The new triply-bridged dinuclear copper(II) complexes, [Cu2(μ-O2CH)(μ-OH)2(dpyam)2](ClO4) · H2O (1), [Cu2(μ-O2CCH3)(μ-OH)(μ-OH2)(dpyam)2](S2O8) (2), [Cu2(μ-O2CCH3)(μ-OH)(μ-OH2)(bpy)2](NO3)2 (3), [Cu2(μ-O2CCH3)(μ-OH)(μ-OH2)(phen)2](BF4)2 · 0.5H2O (4), [Cu2(μ-O2CCH2CH3)(μ-OH)(μ-OH2)(phen)2](NO3)2 (5) and [Cu2(μ-O2CCH3)(μ-OH)(μ-Cl)(bpy)2]Cl · 8.5H2O (6) (dpyam = di-2-pyridylamine, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized and characterized crystallographically and also their spectroscopic and magnetic properties have been studied. A structural classification of this type of dimers, based on the data obtained from X-ray diffraction analysis in the present work and those reported in the literature has been performed. In these complexes, the local geometry around the copper centre is generally a distorted square pyramid and distorted trigonal bipyramid with different degrees of distortion. The global geometry of the dinuclear complexes can be described in terms of the relative arrangement of the two five-coordinate environments, giving rise to different classes (A-F) of complexes. The most logical explanations have been provided for each class describing different magnetic interactions. Practically, there is a clear correlation between structural data and J values of the class B complexes. Extended Hückel calculations were performed for the present complexes 1-6, as well as for some other class B complexes, showing the different molecular orbitals involved in their corresponding frontier orbitals, together with their energy. The results are found to be useful for the proper interpretation and correlation of the magnetic data and the dinuclear structure of the present complexes.

KW - Copper(II) complexes

KW - Crystal structure

KW - EPR

KW - Magnetism

KW - Triply-bridged

UR - https://www.scopus.com/pages/publications/37349031501

U2 - 10.1016/j.poly.2007.09.009

DO - 10.1016/j.poly.2007.09.009

M3 - Article

AN - SCOPUS:37349031501

SN - 0277-5387

VL - 27

SP - 304

EP - 318

JO - Polyhedron

JF - Polyhedron

IS - 1

ER -

New ferromagnetic dinuclear triply-bridged copper(II) compounds containing carboxylato bridges: Synthesis, X-ray structure and magnetic properties

Abstract

Keywords

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