Azide Bridged Dicopper and Dinickel Complexes: Structure and Magnetism
- 1 May 1996
- journal article
- research article
- Published by Informa UK Limited in Comments on Inorganic Chemistry
- Vol. 18 (3), 125-144
- https://doi.org/10.1080/02603599608032718
Abstract
The quest for coordination complexes with novel magnetic properties, which may have potentially useful applications in materials science, has focussed attention on superexchange bridges with the ability to propagate ferromagnetic coupling between paramagnetic transition metal centers. The flexi-dentate azide ligand can bridge two metal centers in two ways, in the μ2-1,1- or μ2-1,3- fashion. In the 1,3-mode superexchange is exclusively antiferomagnetic in nature, whereas in the 1,1-mode the magnetic role of the azide bridge depends in large measure on the angle it subtends at the two metal centers. For dicopper(II) systems with small angles (<108°) ferromagnetic coupling dominates, while at larger angles the azide has been shown to propagate antiferromagnetic exchange. Control of the molecular dimensions, which in turn can influence the geometry at the azide, can lead to control of the magnetic properties. Examples of dicopper(II) and dinickel(II) complexes illustrating the ferromagnetic and antiferromagnetic realms of the azide bridge will be discussed, in addition to the design features of the dinucleating ligands required to bring the two metal centers into juxtaposition in a controlled fashion.Keywords
This publication has 28 references indexed in Scilit:
- Magneto-structural correlations in .mu.2-1,1-azide-bridged dicopper(II) complexes. 2. Dominant antiferromagnetic coupling with azide bridge angles exceeding 108.degree.. X-ray Structures of [Cu2(PAP)(.mu.2-N3)Br3].cntdot.CH2Cl2, [Cu2(PAP6Me)(.mu.2-N3)(.mu.2-Br)Br2].cntdot.1.68H2O, [Cu2(PAP6Me)(.mu.2-N3)(.mu.2-H2O)(NO3)2](NO3).cntdot.0.75CH3OH, [Cu2(PAN)(.mu.2-N3)(.mu.2-NO3)(NO3)2].cntdot.CH3OH.cntdot.CH3CN, and [Cu2(PPD35Me)(.mu.2-N3)Br3(CH3OH)]Inorganic Chemistry, 1995
- Magnetostructural Correlations in .mu.2-1,1-N3 Bridged, Dinuclear Copper(II) Complexes. 1. Ferromagnetic and Antiferromagnetic Coupling Associated with the Azide Bridge. X-ray Crystal Structures of [Cu2(DMPTD)(.mu.2-N3)(.mu.2-Cl)Cl2].cntdot.CH3CN, [Cu2(DMPTD)(.mu.2-N3)2(N3)2], [Cu2(DIP)(.mu.2-N3)(.mu.2-Cl)Cl2].cntdot.0.5CH3OH, [Cu2(PAP46Me-H)(.mu.2-N3)(N3)2].cntdot.0.33H2O, [Cu2(PAP)(.mu.2-N3)Cl3].cntdot.CH2Cl2, [Cu2(PAP)(.mu.2-N3)(N3)(NO3)(CH3OH)](NO3).cntdot.CH3OH, [Cu2(PPD3Me)(.mu.2-N3)Cl3(H2O)1.5], and [Cu2(PPD)(.mu.2-N3)(NO3)3(H2O)1.6]Inorganic Chemistry, 1994
- Syntheses, magnetic properties, and crystal structures of the dimers [LNi(µ-N3)3NiL](ClO4) and [L′2Ni2(N3)2(µ-N3)2](L =N,N′,N″-trimethyl-1,4,7-triazacyclononane; L′= 1,5,9-triazacyclododecane); µ-triazido-vs. µ-diazido-bridgingJournal of the Chemical Society, Chemical Communications, 1985
- Crystal structure and magnetic and EPR properties of bis(.mu.-azido)tetrakis(4-tert-butylpyridine)dicopper(II) perchlorate: a new copper(II) dinuclear complex with a large stabilization of the ground triplet stateInorganic Chemistry, 1984
- Dicopper(II) chloro and azido inclusion complexes of the [24-ane-N2S4] binucleating macrocycle. Synthesis, crystal and molecular structures, and spectral, magnetic, and electrochemical propertiesJournal of the American Chemical Society, 1984
- Crystal structure and magnetic properties of (.mu.-azido)-(.mu.-hydroxo)bis[(N,N,N'N'-tetramethylethylenediamine)copper(II)] perchlorate, a copper(II) dinuclear complex with a large ferromagnetic interactionInorganic Chemistry, 1983
- Dinuclear copper(II) cryptates of macrocyclic ligands: synthesis, crystal structure, and magnetic properties. Mechanism of the exchange interaction through bridging azido ligandsJournal of the American Chemical Society, 1982
- Magnetic exchange interactions in transition-metal dimers. 12. Structural and magnetic characterization of the di-.mu.(1,3)-azido complex [Cu2(Me5dien)2(N3)2](BPh4)2 and similar di-.+-.(1,3)-azido copper(II) dimers. Unusual zero-field splitting in the electron paramagnetic resonance spectraInorganic Chemistry, 1978
- Relation between the singlet-triplet splitting and the copper-oxygen-copper bridge angle in hydroxo-bridged copper dimersInorganic Chemistry, 1976
- Crystal and molecular structure of di-.mu.-azido-bis(2,2',2''-triaminotriethylamine)dinickel(II) tetraphenylborate. Magnetic exchange between azide-bridged octahedral nickel(II) centers. Di-.mu.-azido and mono-.mu.-azido casesInorganic Chemistry, 1975