Magnetic Properties of

Metal complexes
Magnetic properties

• Paramagnetic & diamagnetic:

• Substances (atoms, ions, molecules) with unpaired electrons are
attracted by external magnetic field. They are paramagnetic
substances.
• Those not containing unpaired electrons are repelled by
external mag. field. They are diamagnetic substances.
• Paramagnetic substances , in addition to unpaired electrons,
also contain some paired- electrons in closed shells. Thus, they
also have diamagnetism; but it is small compared to
paramagnetism.
Origin of magnetism
• Magnetic properties are due to the spin (axial ) and orbital
motion (around the nucleus) of electrons in atoms, ions or
molecules.
• Spin and orbital motion of a charged body like electron
produces (induces) a magnetic field.
• This is similar to magnetization of a soft iron core when a
D.C. is passed through an insulated copper coil wound around
the soft iron core.
• But with paired-up electrons, the magnetic fields are cancelled.
• So it is only the unpaired electrons that are responsible for the
observed magnetic properties
• The atoms, ions or molecules containing unpaired electrons
behave as tiny magnets (i e. atomic, ionic or molecular
magnets).
• External strong magnetic field induces magnetic field
in substances.
• In paramagnetic substances, the induced mag. field &
applied (external) mag. field are in the same direction.
So they are attracted by the external mag. field.
• In diamagnetic substances, these fields are in opposite
directions & hence they are repelled by the external
magnetic field.
Paramagnetic substances
• In paramagnetic substances, the tiny magnets (atomic, ionic or
molecular) or mag. dipoles are at random due to thermal agitation.
• In an external mag.field, they tend to align in the direction of the
external field (see diagrams below). But still all are not alligned.
• The magnetic centers (tiny magnets) are sufficiently far apart; they are
separated by diamagnetic centers ( completely filled electron). They are
magnetically dilute materials. They do not interact. There is no
magnetic exchange (spin- spin coupling).
Ferromagnetic & antiferromagnetic substances
• Ferromagnetic substances: These are magnetically
concentrated materials; in these the magnetic centers are very
close to each other ; so the mag. dipoles or mag. moments of
the tiny magnets are strongly coupled; produce strong field..
They are parallel and aligned (oriented) in the direction of the
external field. Retain μ even in the absence of applied field.
Have high susceptibility, χ at ambient (room/ lab) temp.
Antiferromagnetic substances

• Antiferromagnetic substances: These are also magnetically

concentrated materials like ferromagnetic. But the coupling is
antipaprallel; have low susceptibility, χ at ambient (room/ lab)
temp. Antiferromagnetic coupling vanishes above Neel
temp.,TN
Magnetic susceptibility, χ and magnetic moment, µ

• External (applied) magnetic field (H) induces a magnetic field (B) in

paramagnetic materials, given by:

• B = H + 4π I, where I is intensity of magnetization, which is the magnetic

moment per unit volume.

• or B/H = 1 + 4π I/H and P = 1 + 4π κ where B/H = P & κ = I/H ,

• P = B/H , permeability, is the ratio between induced & applied field; P is

+ve & >1 for paramagnetic & -ve for diamagnetic materials

• κ = I / H , is the ratio of intensity of magnetization I to applied field H is

called magnetic susceptibility per unit volume; κ in vacuum is zero.
• κ is +ve for paramagnetic materials.
Magnetic susceptibility, χ and magnetic moment, µ

• Specific susceptibility, χ:
• It is the ratio between volume susceptibility, κ and density, d.
i. e.: χ = κ / d. This is the quantity most frequently measured experimentally.

• Molar susceptibility, χM : Product of specific susceptibility, χ and mol.

weight, M of the substance.
• χM = χ x M.

• Magnetic moment, µ and χM related by,

• χM = N2 µ2 / 3RT.
• Hence, µ = (3RT χM /N2 )1/2 = 2.84 √ (χM T).
• κ & χ have +ve values for paramagnetic substances.

• µ cannot be determined directly; χM is determined first & µ is computed from

the above relation.
Variation of magnetic susceptibility with Temperature
• Temperature affects the magnetic susceptibility χ.
• The magnetic susceptibility, χ is inversely proportional to
absolute temp.: Curie law.
• χ = C/T where C is a constant, Curie const. Curie law is
obeyed by magnetically dilute substances.

• For materials that display magnetic exchange behavior,

Curie- Weis law holds good.
• χ = C/(T- θ) where θ is Weis constant.

• Variation of susceptibility with temp. for paramagnetic,

ferromagnetic and anti -ferromagnetic substances is shown in
the diagram 1.
Curie law plot
Diagram: 1: Variation of χ with T
Variation of χ with T
Variation of χ with T: Paramagnetic materials

• With paramagnetic substances, χ gradually and continuously

decreases with temp. Because increase in temp. further
randomizes the magnetic moments due to thermal agitation. χ
increases if they align in the direction of the applied field &
decreases if align in opposite direction.
Variation of χ with T: Ferromagnetic materials
• There is a sharp decrease in χ up to a temp. known as Curie
temp, TC and there afterwards the behavior is similar to
paramagnetics.
• With ferromagnetic material, the magnetic moments are
coupled and are all aligned in the direction of the applied
magnetic field. Increase in temp. destroys the alignment & so
sharp decrease in χ up to TC point when all the magnetic
moments are decoupled.
Ferromagnetic materials

• The arrangement of magnetic moments in these materials

• beyond Curie point,Tc is now similar to that in
• paramagnetics; so similar behavior beyond this temp.
Variation of χ with T: Antiferromagnetic materials.

• There is a slow increase in χ up to a temp. known as Neel

temp, TN and there afterwards the behavior is similar to
paramagnetics.
• With antiferromagnetic material, the magnetic moments are
coupled and are opposed to the applied magnetic field; so low
χ at room temp.
• With increase in temp. the magnetic moments are decoupled &
are aligned with the external field; so initially χ increases with
temp. up to TN where all the magnetic moments are decoupled.
• Above TN temp., the thermal agitation randomizes the
magnetic moments similar to paramagnetics. (see next slide)
Antiferromagnetic materials
Determination of Magnetic moment, µ

• µ cannot be determined directly. But the magnetic susceptibility per unit

volume κ, can be measured experimentally; from this χ , χM & from the χM
corr
the magnetic moment, µ is calculated using the relation:
• µ = 2.84 (χM corr T)1/2.

• Gouy Method:
• This method involves determining the apparent increase in weight, Δw of
a paramagnetic material in a magnetic field; this is related to the
susceptibility:
• Δw = ½(κ1 – κ2) H2A, …….. 1. where
• κ1 = volume susceptibility of the sample,
• κ2 = volume susceptibility of air; it is const = 0.029 x 10-16 cgs units cm-3.
• H = applied magnetic field strength,
• A = cross sectional area of the test sample.
Determination of Magnetic moment, µ

• Δw = ½(κ1 – κ2) H2A, … 1. can be rearranged as

• (κ1 – κ2) = 2* Δw / H2A or κ1 = κ2 + 2* Δw / H2A
• The value of κ2, is const = 0.029 x 10-16 cgs units cm-3.,
• So κ’1 = 2* Δw / H2A , where κ’1 is corrected volume
susceptibility of the sample.
• Δw is obtained by the difference in weights the sample with
the magnetic field off and on.
• The magnitude of H2A depends on the set of apparatus used.
• It is obtained by calibrating the apparatus using a standard with
accurately known κ or χ .
• Example: Hg[Co(NCS)4], χ = 5.92 X 10-6cgs units cm-3.
• CuSO4 5H2O, χ = 16.44 X 10-6cgs units cm-3.
Determination of Magnetic moment, µ: Guoy Method
• The apparatus used in Guoy method consists of a sensitive
balance, a powerful electromagnet of strength ~ 10,000 gauss, a
thin Pyrex glass sample tube ( 8- 10mm length, ~ 3mm inner
dia). The assembly is kept in an air-tight chamber. (See figure
below).
Determination of Magnetic moment, µ
• Guoy balance
Determination of Magnetic moment, µ: Guoy Method
Determination of Magnetic moment, µ: Guoy Method

• The finely powdered sample is packed uniformly in the tube.

• Using a thin quartz fiber, it is suspended from the balance
between the poles of the electromagnet.

• The sample is weighed with field off (w1) & on (w2). The
sample is attracted downwards by the magnetic field & so
weighs more, w2 > w1. 3 to 4 values of change in weight Δw =
w2 - w1 are taken & the average value is used in calculations.

• The downward pull, F = Δw = ½(κ1 – κ2) H2A, where

• κ1 = κ2 + 2Δw / H2A………… 2.

• κ2 , vol. susceptibility of air is known, but the field strength, H

& cross- sectional area, A are not known.
• H & A are constant for a given set of apparatus.
Determination of Magnetic moment, µ: Guoy Method

• A standard substance of accurately known susceptibility (χM

std ) is used to calibrate the apparatus; i. e to find H & A.

• Example: Hg[Co(NCS)4], χ = 5.92 X 10-6cgs units cm-3.

• CuSO4 5H2O, χ = 16.44 X 10-6cgs units cm-3.
• κstd = κ2 + 2Δw / H2A;
• χM std = κstd *Mstd /d = Mstd /d [2Δw / H2A], ……… 3.
• d, is obtained from d = wstd /v, where wstd is weight of std & v
is its volume is volume.
• Volume, v is determined by dividing the weight of water filled
up to the mark in the sample tube by density of water.
• H2A is deduced from eqn 3 where all other terms are known.
H2A = Mstd /d [2Δw / χM std ]
Determination of Magnetic moment, µ: Guoy Method

• Then by measuring Δw for the test sample in the calibrated apparatus,

its volume susceptibility κ1 is calculated.
• Then, molar susceptibility, χM = κ1 * M /d = M/d [2Δw / H2A], where
M = mol.wt., d = density.
• The density, d of sample is determined by dividing weight of sample
(w1) by volume, v.
• χMcor : χM has to be corrected for diamagnetism of ligands & ions. The
χM obtained from weight change, Δw is the net magnetism i.e.: χM = χ
paramag + χdiamag.

• So χMcor = χ paramag - χdiamag.

• χdiamag is obtained from Pascal's constants.
• Then µ is obtained from: µ = 2.84[χMcor .T ]1/2 .
Spin and orbital magnetic moments (µS & µL )
• The paramagnetic moment µ, originates from in the spins & orbital
motions of the unpaired electrons in the substance.
• There are three possible modes of coupling between these : spin-spin
(s- s), orbital- orbital (l- l) and spin- orbital (l- s).
• For some complexes, like those of lanthanides, all the three types of
couplings are important.
• And the paramagnetic moment, is given by: µ = g[J(J+1)]1/2 , where
• J is total angular momentum quantum number & g is the Lande
splitting factor for the electron.
• g = 1+ J(J+1) + S(S+1) – L(L+1) / 2J(J+1)
• And J = (L+S), (L+S -1) (L+S -2),…|L- S|
• For some complexes, the spin- orbit coupling is negligible and spin &
orbital contributions are significant.
• For these the magnetic moment is given by :
• µ =[4S(S+1) + L(L+1)]1/2 .
• Spin magnetic moment, µs : It is due to the spins of the unpaired
electrons present .
• It is given by µS= √ 4S(S+1) where S = ∑ ms, total electron spin. For
each electron, s=1/2; so for ‘n’ electrons, S=1/2 * n.
Thus, µS = √ n(n+2)
• Orbital mag. Moment, µL : It is due to the orbital motion of
unpaired electrons around the nucleus; it is given by:

• µL = √L(L+1), where, L = ∑ ml, total orbital moment.

• So total mag. moment: µS +L =

• But very often, in metal complexes, there is no full contribution from

µL , it is partly or fully quenched. This is due to the presence
ligands ( ligand- field) in complexes.
High spin & low spin complexes:

• During complex formation, with strong ligands, electron (d /f)

pairing occurs in some complexes if Δ > P. These are low spin
complexes.
• Example: [Fe(CN)6]4- d6, ion, CN- is strong ligand, Δ >P spins
paired, & so, it is a low spin complex; all electrons paired t2g6; so
diamagnetic.
• But with [Fe(H2O)6]2+, H2O is weak ligand, so Δ< P; no spin pairing;
(t2g)4 (eg)2 has 4 unpaired electrons similar to free Fe 2+ ion. So µS = √
4(4+2) = 4.8989.
Orbital magnetic moment, µL

• For µL to arise, the electrons in the complex must

move from one orbital to other around the nucleus
of the metal ion. They can move from one orbital to
other only if:

• 1. The orbitals are degenerate( identical energy).

• 2. They are transformable by rotation around the axis.
• 3. They do not contain same number of electrons.
Orbital magnetic moment, µL

• But in complexes, the ligands split the orbitals &

remove the degeneracy.

• Thus, oct. field splits the d- orbitals into t2g & eg sets of
different energy. In the eg set, dz2 & dx2 – y2 orbitals are
not transformable by rotation around any axes. So the
eg set does not contribute to µL .

• The t2g orbitals are degenerate & contribute to µL if

they do not contain same number of electrons (half-
full or completely filled, i.e. d3 or d6).
Orbital magnetic moment, µL

• Thus, the following configurations have no µL contribution to µ for

eff
oct. complexes.
• h. s. complexes:
• t2g 3 (ground state 4A2g); t2g 3 eg1 (ground state 5Eg);
• t2g 3 eg2 (ground state 6A1g); t2g 6 eg2 (ground state 3A2g);
• t2g 6 eg3 (ground state 3A2g);
• l. s. complexes:
• t2g 6 (ground state 1A1g); t2g 6 eg1 (ground state 2Eg).

• It can be seen that no µL contribution to µeff for configurations with

A or E ground state terms.
Orbital magnetic moment, µL

• The following configurations have µ contribution to µeff for oct.

L
complexes.
• t2g 1 (ground state 2T2g); t2g 2 (ground state 3T1g);
• t2g 4 (ground state 3T1g); t2g 2 (ground state 2T1g).

• There is µL contribution to µeff for configurations with T ground state

terms.
Orbital magnetic moment, µL …..

• Example: [V(H2O)6]3+ ,a d2 ion with (dxy)1, (dyz)1, (dzx)0 configuration..

• The t2g orbitals are degenerate, transformable by rotation by 45o
around the axes & they do not contain same number of electrons. So,
it fulfills all the three conditions and contributes to µL .
• Its µS = [ 2(2 + 2)] ½ = (8)1/2 = 2.828.
• µL = [3(3 +1)]1/2 = (12)1/2 = 3.464
• µS + µL = 2.828 +1.414 = 6.292BM
• But observed mag. moment µeff , is less,
• µeff = 2.75 – 2.85 B.M. which is very close
• to µS only.
Orbital magnetic moment, µL …..

• [ Cr(H2O)6]3+, a d3 ion with (dxy)1, (dyz)1, (dzx)1 configuration, has

µL = 0, since it has the same number of unpaired electrons in
the degenerate orbitals. µS =[3(3 + 2)]1/2 = (15)1/2 = 3.873 BM
• [ Co(H2O)6]2+, a d7 ion with (dxy)2, (dyz)2, (dzx)1 configuration,
has µL contribution.
• µS =3.873 BM, µL = [3(3 +1)]1/2 = (12)1/2 = 3.464 BM;
• hence µS + µL = 3.873 + 3.464 = 7.287BM.
• But observed mag. Moment, µeff is less : it is 4.3 - 5.3BM
• For [ Mn(H2O)6]2+, a d5 ion, has (dxy)1, (dyz)1, (dzx)1 (dx2 –y 2)1 (dz2)1
configuration since Δ < P; high spin complex.
• µS = [ 5(5 +2)]1/2 = (35)1/2 = 5.916 BM ; µL = 0 .
• Experimentally observed moment, µeff is ~ 5.92 BM.
• Also for h. s. oct. Fe3+ (d5)complexes, µeff is ~ 5.92 BM.