Magnetic

Properties of
Transition Metal
Metal Complexes

Syllabus
Guoy’s and Faradays’s method for the
determination of magnetic susceptibility,
calculation of magnetic moments,
paramagnetism, diamagnetism,
ferromagnetism, anti-ferromagnetism,
temperature-independent paramagnetism;
Curie law, Curie-Weiss Law. Classification of
paramagnetic complex ions, Spin only group,
Group with large multiplet separation, Group
with small multiplet separation spin-orbit
coupling, quenching of orbital angular
momenta, spin cross over the phenomenon,
applications of magnetic data in the
structural studies of complexes.

Dr. Asha T. M.
Paramagnetic materials and Curies’s Law
These materials contain one or more unpaired electrons and paramagnetsim is temp.
dependent. Magnetic properties of many materials were first studied by Curie and he found
that ‘paramagnetic susceptibility’ χp is inversely proportional to absolute temp.

χp = C/T

C = Curies’s constant and is characteristic of the substance. β

This is known as Curies’s Law, which states that the magnetic susceptiblity of a paramagnetic
material is inversely proportional to temperature.

Later, Classical mechanics was applied to paramagnetism in gases and was found that For
free electron in a metal Curies’s constant would be,

nμ2B
C=
K
Hence the above equation becomes,

𝐧𝛍𝟐𝐁
∴ χp =
𝐊𝐓
Therefore by substituting the value of n, μB, K and T, χp can be obtained for any material. But
value obtained in this way is hundred times larger compared to the value obtained
experimentally.

This can be explained using Fermi Dirac statistics.

Temperature Independent Paramagnetism

Some substances exhibit temperature independent paramagnetism (TIP) that arise as a result
of coupling between the magnetic ground state and non thermally populated excited state.
The distribution of electrons in a metal at the absolute zero of temp. is shown in Figure
a below by plotting density of state [N(E)] as a function of energy (E). In the absence of
external magnetic field, electrons occupy all the available states having energies less than the
Fermi energy (EF). They are shown divided into two groups, according as their spins are
parallel (minus) and antiparallel (plus).
When an external field is applied, magnetic moment due to the spins line up either
parallel or antiparallel to the field. Electrons which have antiparallel moment undergoes a
shift in energy +βH as shown in Figure b.
This situation is unstable and at equilibrium, some of the electrons in the antiparallel
state undergo transition to the energy parallel states. This leads to a situation shown in Figure
c. This is the situation at absolute zero.

DR. ASHA T. M. 1
At any finite temperature T, only the electron in the vicinity of EF and falling the range ~ KT
can respond to the external magnetic field. Therefore only a fraction (KT/EF) of the total
number of electrons contribute to the paramagnetic susceptibility.

𝐧𝛍𝟐𝐁 𝐊𝐓 𝐧𝛍𝟐𝐁
∴ χp = 𝐱 =
𝐊 𝐄𝐅 𝐄𝐅

This shows that susceptibility is virtually independent of reasonable changes in temperature.

Curie-Weiss law
Curie point, also called Curie Temperature, is the
temperature above which a ferromagnetic material
behaves like a paramagnetic material. It is also the
minimum temperature at which a ferromagnetic
sucbstance is converted into paramagnetic substance.
The Curie-Weiss law describes the magnetic
susceptibility χ of a ferromagnet in the paramagnetic
region above the Curie point:
𝑪
χ=
𝑻− ѳ
Where C is a material-specific Curie constant, T is the absolute temperature, and ѳ is
the Curie temperature, both measured in kelvin.

Magnetic moment
The origin of magnetism in an atom lies in the motion of its negatively charged electrons. The
overall magnetic moment of an atom is the resultant of magnetic moment generated by the
orbital motion of electrons called the “orbital magnetic moment” (μl) and the magnetic
moment generated by the spin motion of electrons called the spin magnetic moment” (μ s).

DR. ASHA T. M. 2
Orbital magnetic moment” (μl)

A negatively charged electron moving in a circular orbit generates a magnetic field in a

direction perpendicular to the plane of orbital containing the electron. The moment of
magnetic field so generated is called the orbital magnetic moment.

It is given by:

μl = [l(l + 1)]1/2 B.M.

l = Orbital angular momentum quantum number

Spin magnetic moment” (μs)

The negatively charged electron moving in its spin motion will also produce a magnetic field
whose moment is directed alomg the spin axis. The moment of magnetic field so generated
is called the spin magnetic moment.

It is given by:

μl = g [s(s + 1)]1/2 B.M.

g = Lande splitting factor

s = Spin angular momentum quantum number

The overall magnetic moment, μ for a multielectron system will be a resultant of μ l and μs.
There are three possible modes of coupling between these components: spin-spin, orbital-
orbital ans spin-orbital.

Classification of paramagnetic complex ions

➢ For some complexes, particularly those of lanthanides, we must consider all the three
types of coupling. The theoretical ‘paramagnetic moment’ (which originates in the
spins and orbital motion of the unpaired electrons in the substance) for such a
complex is given by:
μ = g [J(J + 1)]1/2 B.M.
Where, J is the ‘total angular momentum quantum number’ and g is the Lande
splitting factor for electrons.
J(J+1)+S(S+1)−L(L+1)
g = Lande splitting factor ; g = 1 +
2J (J+1)
The value of J depends on the total orbital angular momentum quantum
number, L and total spin angular momentum quantum number, S.

➢ For complexes in which spin-orbit coupling is non-existent or negligible, but spin and
orbital contribution are both significant, the predicted expression μ for is,
μ = [4S(S + 1) + L(L+1)]1/2 B.M.

DR. ASHA T. M. 3
 But the above equation describes a condition that is never fully realized in complexess
because, the actual orbital contribution is always somewhat less than the ideal value.
This occurs because the orbital angular momentum is reduced from what it would be
in the free metal ion by the presence of ligands.

➢ In an extreme case, where L is effectively zero, the orbital contribution to magnetic

moment is said to be ‘quenched’. Quenching is caused by the restriction of the orbital
motion of the electrons by the influence of strong ligand fields. The ligand field in
these comlexes are greater than the spin-orbit interactions.
This is the general situation in complexes having A or E ground states, which
would include octahedral d1,d4 (hs), d5(hs), d6(ls), d7(ls) and d8 cases. Furthermore,
when a complex inviolves a first row transition element, even if the ground state is T,
the orbital contributiuon generally may be ignored.
For L = 0 condition, μ is given by
μ = [4S(S + 1)]1/2
= [n(n + 2)]1/2 B.M
Where, S = n/2 and n = number of unpaired electrons. The above formula is known as
the ‘spin only formula’ for magnetic moment.

➢ For certain complexes, which magnetic moment value show deviation from spin only
formula. This shows that the there is considerable ‘spin-orbit coupling’.
𝛂𝛌
μ = μs [1 - ] B.M
𝚫
Where, α is a constant denoting the spectroscopic state of ion in the ligand field.
Δ = seperation energy between the ground level being mixed.
λ = is the spin -orbit coupling constant per electron.
The value λ of can be obtained from the difference in energy between states of
different J values.

Orbital contribution to magnetic moment

The observed moments of high spin complexes of first row transition metals are in good
agreement with the calculated spin only magnetic moment. However such agreements are
absent in few cases. For example, Co(II) complexes, the observed μ is higher than that
calculated by spin only formula. This enhanced moment is due to orbital contribution to the
magnetic moment.
When it is possible to transform an orbital into an equivalent (degenerate) orbital by
rotration, then an orbital angular momentum arise. Example.: t 2g orbitals (dxy,dxz,dyz) by
rotation via 900 can be interconverted since these three orbitals have same shape, though
with different orientation in space. But the eg orbitals (dx2-y2 and dz2) have different shape and
cannot be interconverted.

DR. ASHA T. M. 4
However if t2g orbitals are singly occupied by an electron each, then the dxy orbital cannot be
transformed into dxz or dyz, since latter two already contains an electron each with the same
spin. Similarly doubly occupied t2g orbital also cannot be interconverted. Therefore,
configuration with have t2g3 and t2g6 have no orbital contribution.

In Oh high spin, the following systems have orbital contribution.

t2g1eg0, t2g2eg0, t2g4eg0, t2g5eg0

In Td geometry, the following have orbital contribution.

e2 t21, e2 t22, e4 t24, e4 t26

Group with large multiplet separation

For lanthanides, the paramagnetic character is due to the
unpaired electrons in f shell. Here the unpaired electrons are
well shielded from external ligand field (not exposed to
environment) or covalent bonding forces, and the spin orbit
coupling is very large. The ground state is very well separated
from the next excited state, by an energy difference which is
large, compared to KT (200 cm-1) (Figure). Therefore only
ground state is populated and not the excited state (because
thermal energy cannot promote the electrons to excited
state). Under these circumstances spin orbit coupling is
significant and for a given state of L+S, J-will take all values
from L+S to L-S.

The magnetic moment in this case is given by:

μ = g [J(J + 1)]1/2 B.M.

In actinides, R-S coupling or L-S coupling is inadequate for actinides, so we have to go

for j-j coupling. In the case of actinides the 5f electrons are not deeply seated but to some
extent affected by the external field. So it is difficult to explain.

Small multiplet separation

For d-block elements, the 4s and the next orbitals lie close in
energy and the difference in energy is comparable with KT at
room temperature. Therefore both levels are equally populated
therefore the effect of spin orbit coupling is small. So one can
ignore the coupling and treat L & S as to interact independently
with external field.

The magnetic moment in this case is given by:

DR. ASHA T. M. 5
 μ = [4S(S + 1) + L(L+1)]1/2 B.M.

In transition metals, the orbital contribution is quenched with the result of spin contribution.
Thus only the spin angular momenturm determines the magnetic moment.

Spin only formula: μ = [4S(S + 1)]1/2 = [n(n + 2)]1/2 B.M

Spin only formula hold good only for I-row of transition series.

Spin cross over phenomenon

Spin Crossover (SCO), sometimes referred to as spin transition or spin equilibrium behavior,
is a phenomenon that occurs in some metal complexes wherein spin state of the complex
changes due to external stimuli such as a variation of temperature, pressure, light irradiation
or an influence of a magnetic field.

Spin crossover refers to the transitions between high to low, or low to high, spin states. This
phenomenon is commonly observed with some first row transition metal complexes with a
d4 -d7 electron configuration in octahedral ligand geometry. Metal ions with any of the d 4, d5,
d6 and d7 configuration exhibit two possible electron configurations (the high spin and low
spin state) in the octahedral ligand field. These high spin and low spin states of an octahedral
complex will have the same energy when Δ = P. If in a coordination complex the crystal field
splitting is close to the Δ = P value, then the energy difference between the two spin states of
the complex will be in the range of thermal energy KT. Further, in octahedral field, if the
energy of the two spin states is same or nearly same, the low spin and high spin states can
coexist in equilibrium. This phenomenon is referred to as spin-state equilibrium; the magnetic
moment for these complexes will be anomalous.
An example of metal ion that can exist in HS or LS state in octahedral ligand field is
Fe . Fe3+ can attain a LS or a HS state and this is decided by the nature of ligands that are
3+

coordinated to the given complex, as in Figure below.

Consider the low spin complex, [Fe(CN)6]4-(ground state 1A1g) and the high spin complex,
[FeF6]4-(ground state 5T2g) of Fe2+ ion (figure below).

DR. ASHA T. M. 6
Now, change in the temperature will lead to an alteration in the population of the two spin
states. The diagram of the two complexes given below reveals that if the ground state of the
complex is low spin, then

1. An increase in temperature will increase in the population of the high spin state, i.e.,
the magnetic susceptibility will increase, and
2. A decrease in temperature will increase in the population of the low spin state, i.e.,
the magnetic susceptibility will decrease.

On the other hand, if the ground state is high spin then the reverse of (1) and (2) will hold
true.

Spin Transition Curves

Spin crossover phenomenon can be represented by spin transition curves. In spin transition
curves, T is plotted verses high-spin molar fraction, γHS. The figure below shows a gradual spin
transition (left) and an abrupt transition with hysteresis (right). For a transition to be
considered gradual, it typically takes place over a large temperature range, even up to several
hundred K, whereas for a transition to be considered abrupt, it should take place within 10 K
or less.

γHS is calculated as follows:

Applications of magnetic data in the structural studies of complexes

Magnetic moment values can be used for structural elucidation of metal complexes. For
example, by knowing the value of magnetic moment, we can predict the structure of a

DR. ASHA T. M. 7
complex. For example, consider a complex, [NiL4]2-, where L is a monodentate anionic ligand.
By measuring the magnetic moment value, we van arrive at the geometry of the complex.
Since the complex is a four-coordinate complex, the two possible geometries are Td
and square planar one. Metal ion is Ni2+, which is having d8 configuration. Now consider d
electronic distribution both the geometries.

Since in this case of square planar geometry, there is no unpaired electron, so it has zero
magnetic moment. But in Td geometry, presence of two unpaired electron results in a net
magnetic moment.

Example.: Consider two complexes, [NiCl4]2- and [Ni(CN)4]2-. The magnetic moment values of
two complexes are 2.82 BM and 0 BM respectively. This indicates that the geometries of
[NiCl4]2- and [Ni(CN)4]2- are Td and square planar respectively.

DR. ASHA T. M. 8