Lecture 19 Magnetic properties and the Nephelauxetic effect.ppt

Lecture 19: Magnetic properties and the Nephelauxetic effect Magnetic properties Magnetic susceptibility (μ) and the spin-only formula. Materials that are diamagnetic are repelled by a magnetic field, whereas paramagnetic substances are attracted into a magnetic field, i.e. show magnetic susceptibility. The spinning of unpaired electrons in paramagnetic complexes of d-block metal ions creates a magnetic field, and these spinning electrons are in effect small magnets. The magnetic susceptibility, μ, due to the spinning of the electrons is given by the spin-only formula: μ(spin-only) = n(n + 2) The spin-only formula applies reasonably well to metal ions from the first row of transition metals: (units = μB,, Bohr-magnetons) Metal ion dn configuration μeff(spin only) μeff (observed) Ca2+, Sc3+ d0 0 0 Ti3+ d1 1.73 1.7-1.8 V3+ d2 2.83 2.8-3.1 V2+, Cr3+ d3 3.87 3.7-3.9 Cr2+, Mn3+ d4 4.90 4.8-4.9 Mn2+, Fe3+ d5 5.92 5.7-6.0 Fe2+, Co3+ d6 4.90 5.0-5.6 Co2+ d7 3.87 4.3-5.2 Ni2+ d8 2.83 2.9-3.9 Cu2+ d9 1.73 1.9-2.1 Zn2+, Ga3+ d10 0 0 Example: What is the magnetic susceptibility of [CoF6]3-, assuming that the spin-only formula will apply: [CoF6]3- is high spin Co(III). (you should know this). High-spin Co(III) is d6 with four unpaired electrons, so n = 4. We have μeff = n(n + 2) = 4.90 μB For the first-row d-block metal ions the main contribution to magnetic susceptibility is from electron spin. However, there is also an orbital contribution from the motion of unpaired electrons from one d-orbital to another. This motion constitutes an electric current, and so creates a magnetic field (see next slide). The extent to which the orbital contribution adds to the overall magnetic moment is controlled by the spin-orbit coupling constant, λ. The overall value of μeff is related to μ(spin-only) by: μeff = μ(spin-only)(1 - αλ/Δoct) Diagrammatic representation of spin and orbital contribut