Chemistry 3820 Lecture Notes

Dr. M. Gerken

Page67

7. Introduction to Magnetochemistry
Many transition-metal complexes are paramagnetic, due to the presence on unpaired d electrons. Ligand field theory can be used to account for the number of unpaired d electrons that occur for any specific compound. The underlying principles of ligand field theory have already been developed. In particular, magnetic measurements can distinguish between two possible arrangements of the d electrons in the common Td and Oh geometries, called high-spin and low-spin. For example, Figure 7-1 illustrates the consequences of the two environments for an octahedral d5 system. Typically, high-spin complexes occur when the size of 0 is of the same order of magnitude as the electron spin-pairing energy.
OCTAHEDRAL - HIGH SPIN OCTAHEDRAL - LOW SPIN

eg

eg

0
t2g t 2g

Figure 7-1 Ligand field splitting diagram for high and low spin octahedral environments

However, when 0 >> spin-pairing energy, the low-spin arrangement will be preferred. For any given metal and oxidation state, the size of 0 is largely determined by the nature of ligand, and especially of the identity and charge of the donor atoms in the ligands. Magnetochemistry can be used to distinguish the two cases 7.1 Bulk magnetic behaviour Much of van Vleck's early work on crystal field theory focused on interpreting the magnetic behaviour of transition-metal compounds (which of course include the most important bulk magnetic materials such as iron, cobalt, and magnetite, Fe3O4). The origin of all magnetic phenomena can be traced to the motion of charges. Electrons moving in a circular path in an atom or molecule are constantly undergoing acceleration (because of the circular motion), and therefore, generate a magnetic field perpendicular to their direction of motion, the orbital magnetic moment. Electrons also have a spin, as a simplification visualized by the rotation of the electron around its own axis, which produces a spin magnetic moment. If the electrons are paired in a wavefunction, their spin magnetic fields are equal and opposite (spin paired). If these moving electrons are placed into a large external magnetic field (the applied magnetic field), then the external field induces an additional current that causes a magnetic field by itself. This induced magnetic field is opposite to the external magnetic field (Lenz law). As a consequence, the magnetic field (actually, B is the magnetic flux density, H is the magnetic field strength) inside the sample (Binternal) will be weaker than the external field (Bexternal) (see figure on the right-hand side), with B being negative, and the sample is repelled by the applied field. Binternal = Bexternal + B This magnetic behaviour is called diamagnetism. Every paired electron contributes to the diamagnetism of a substance. Hence, diamagnetism is present in every sample. The equation can be rewritten in two different ways: with r as the relative magnetic permeability Binternal = r Bexternal or Binternal = (1+ V) Bexternal and B = V Bexternal with V as the magnetic susceptibility (volume susceptibility) The formulation using susceptibilities is more commonly used among magnetochemists and will be used in this course. For diamagnetic samples, V is negative. The size of the diamagnetic susceptibility is a function of (i) the number of electrons and (ii) the radius of the electron orbits. Instead of the additional magnetic flux density, B, the magnetization M (in A/m) is generally used: B = 0 M (0 is the magnetic field constant). With Bexternal = 0 Hexternal substitution the above equation yields M = V Hexternal.

Chemistry 3820 Lecture Notes

Dr. M. Gerken

Page68

If an orbital is singly occupied, a small magnetic moment is associated with the unpaired electron. This magnetic moment aligns itself with an external magnetic field and increases the magnetic field inside the sample (see figure above). As a consequence, this sample is drawn into the magnetic field. This effect is called paramagnetism. This causes a net attraction between paramagnets and magnetic field gradients. The paramagnetic contribution is two orders of magnitudes larger than the diamagnetic contributions. Therefore, one unpaired electron as a paramagnetic centre will overshadow the diamagnetism of all the paired electrons in the sample. For paramagnetic substances, B and the paramagnetic susceptibility are positive. Macroscopic magnetic effects are caused by the additive (cooperative) effect of atomic paramagnets. If every second paramagnet in a material is aligned in an opposing fashion, the bulk material is said to be antiferromagnetic. If on the other hand they align in the same direction, the bulk material is ferromagnetic. Permanent iron magnets are common examples of ferromagnetic materials. The magnetic susceptibility is a measure of the force with which magnetic attractions or repulsions occur. The relevant scale in the old, but commonly used cgs units of magnetic susceptibility is given in Table 7-1. The susceptibilities in SI units and cgs units differ by a factor of 4: (SI) = 4 (cgs). Table 7-1 Classification of Magnetic Behaviour Type of magnetism Diamagnetism Paramagnetism Ferromagnetism Antiferromagnetism Susceptibility, (cgs units) -10-6 100 10
-6

Field dependence Independent of H Independent of H Dependent on H Often dependent on H

10-2 to 10-4 1 to 100 10

The total magnetic susceptibility of the substance is the sum of all the diamagnetic and paramagnetic contributions from all the electrons in the sample. When these are oriented at random, the measurement of the bulk sample is akin to measuring the = dia + para average susceptibility of a single formula unit. Measurements are usually made on finely ground powders, which can safely be assumed to be totally randomly distributed. The volume susceptibility, V, is defined by the equation:

F = 0 V V H

dH dx

The integration of this equation relates the force, F, experienced by the sample over the integrated field strength. Since weighing a sample is equivalent to measuring the force of gravity acting on it, we can use the weight of the sample compared to its apparent weight in a magnetic field to measure . Rather than solving this equation directly, which would require the difficult job of measuring the integrated field strength over the volume of space the sample occupies, we use a standard of known measured under identical conditions to get for our unknown material. A common standard is HgCo(SCN)4 with M = 16.44 10-6 cm3 mol-1 (cgs units) at 20 C. For such measurements, we use a Gouy balance, where the sample is weighed underneath the balance and placed between the poles of a magnet, which can be turned on and off. Several of the seemingly laborious restrictions result directly from this theory: (1) the tube must always be suspended at exactly the same height, and the contents must always be filled to exactly the same level - otherwise the integrated field strength will not be the same. (2) Air contains paramagnetic oxygen, and glass always contains some paramagnetic impurities. Therefore the tubes themselves must be carefully calibrated, and the volume of the displaced air must be accounted for. This is due to the 100-fold greater susceptibility of paramagnetic versus diamagnetic substances. It is possible to ascribe paramagnetism to a diamagnetic substance if these corrections are not made! 7.2 Diamagnetic susceptibility correction We have to distinguish between the volume susceptibility, V, from the molar susceptibility, M [cm3 mol-1], which is related to gram susceptibility (i.e. specific susceptibility) g [cm3g-1] by the molar mass. The gram susceptibility is related to V [dimensionless] by the density. g = V/ M = g M As stated above, M is positive if the substance is paramagnetic, and negative if it is diamagnetic. Since the unpaired electrons in a metal complex are usually only due to a few electrons in a large molecule, the sum of all the diamagnetic effects can be

Chemistry 3820 Lecture Notes

Dr. M. Gerken

Page69

substantial. Fortunately the diamagnetic contribution is additive, so that the paramagnetic term paraM can be extracted according to the following formula: totalM = paraM + diaM(metal core electrons) + diaM(ligands) + diaM(ions) + diaM(solvate) Diamagnetic correction terms are tabulated in several textbooks (often called Pascals constants) and fortunately additivity of the separate components of the molecule can be used. The diamagnetic susceptibility is independent of temperature. 7.3 Microscopic theory of paramagnetism For a substance consisting of non-interacting paramagnetic centers (a condition which coordination compounds approximate much better than most other magnetic materials due to the insulating effect of the surrounding ligands), the magnetic susceptibility (paramagnetic susceptibility) varies with temperature according to the Curie Law: M = C/T where C is the Curie constant. With increasing temperature, the magnetic moments (electrons) will move more randomly, lowering the paramagnetic contribution. Usually, -1 is plotted against T, producing a straight line with positive slope. In comparison, diamagnetism does not exhibit any temperature dependence. For substances which follow the Curie law closely, the effective magnetic moment is given by:

eff

para eff = 2.84 ( M T)

para 3k M T = 2 N A

1/ 2

1/ 2

Here is the Bohr magneton ( =

eh = 9.274 10-24 J T-1), k is the Boltzmann constant and NA is Avogadro's number. 2 mc

Substituting the constants gives the second term, which gives eff in units of Bohr magnetons when paraM is expressed in cgs units. Strictly, we would have to consider the spin as well as the orbital components (or some sort of coupled angular momentum) for the prediction of paramagnetism. In a 3d transition-metal complex, the electric field of the ligands (the ligand field) usually quenches the orbital contribution to the paramagnetism. Therefore, we can make the assumption that only the spin angular momentum of the electron, and not its orbital angular momentum, contributes to paraM. Using the number of unpaired electrons, n, the spin-only magnetic moment can be calculated from the equation, with given in Bohr magneton : = 2 {S(S + 1)} Since S represents the overall spin quantum number, and each electron has a value of , we can rewrite the first equation in terms of the total number of unpaired electrons: = {n(n + 2)} Thus the approximate value of the magnetic moment of any transition metal immediately gives us the total number of unpaired electrons. There are some important deviations from this simplified theory. Calculated spin-only magnetic moments Materials whose magnetic moments are not so well insulated from one another often follow a modified temperature dependence called Ion N S / / the Curie-Weiss Law. Also many metal complexes have appreciable Calculated Experiment orbital angular momentum contributions to the magnetic moment. Especially, 4d and 5d transition-metal complexes deviate significantly 3+ Ti 1 1.73 1.7-1.8 from the spin-only value. V3+ 2 1 2.83 2.7-2.9 The table on the right-hand side lists experimentally determined and calculated magnetic moments. The good agreement between the 3+ 3 3/2 3.87 3.8 Cr experimental value and the calculated spin-only value shows that the 3+ 4 2 4.90 4.8-4.9 Mn assumption of a quenched orbital momentum is valid for these cations. 5 5/2 5.92 5.9 Fe3+ The magnetic moment of [Mn(NCS)6]4- has been determined as 6.06 Bohr-magnetons. Predict the electron configuration. Although the agreement in the above table is excellent, some complexes have measured moments which are in poorer agreement. For example, [Fe(CN)6]3- has =2.3 BM. This is directly between the 1.7 and 2.8 BM predicted for one and two unpaired electrons, respectively. Since the cyano ligand is a strong-field lignad we expect an electron configuration of (t2g)5 with one unpaired electron. The greater-than-expected magnetic moment is explained by the contribution of orbital angular momentum. Crudely speaking, this implies that the unpaired electron is circulating through the orbitals of the complex, and the motion of this charge is inducing a magnetic moment. Conditions for this to occur are fulfilled in Oh complexes with 3d1, 3d2, and low-spin 3d4

Chemistry 3820 Lecture Notes

Dr. M. Gerken

Page70

and 3d5 configurations. Significant orbital contributions occur for 4d, 5d, and 4f electron configurations, so we will non consider theses any further at this time. 7.4 Bulk magnetism Bulk magnets consist essentially of aligned paramagnets. Normally entropy ensures that atomic paramagnets are randomly arranged, and there is no bulk magnetization. However, in certain solids the individual magnetic moments do line up. They may either line up in alternating arrays, which is called antiferromagnetism, or in collinear arrays, which is ferromagnetism as seen in common bar magnets.