SECOND SEMESTER 2022-23

Course No. : CHEM F343

Course Title : Inorganic Chemistry-III
Instructor-in-charge : Prof. Halan Prakash
Instructor : Dr. Sudipta Chatterjee
1. Scope and Objective of the Course: Molecular Magnetism - general properties. Origin of Magnetism. Electronic spectra and magnetic
properties in Transition metal complexes. Other emerging topics in inorganic chemistry.

2. Text Book: T2. Huheey J. E., Keiter, Ellen A., and Keiter, Richard L., Medhi, O.K.“Inorganic Chemistry”, 4th ed., Pearson Education,
Fifth Indian Reprint 2006; T3. R. L. Dutta and A. Syamal; Elements of Magnetochemistry, 2nd Edition, EWP New Delhi, Reprint 2021.
Reference Books: R1: J. D. Lee; Concise Inorganic Chemistry, Fifth Edition, Wiley, Reprint 2021; R2: R. Sarkar; General and
Inorganic Chemistry (Part II), New Central Book Agency (P) Ltd., Reprint March 2005; Journal articles.

Topics Chapter & Pages # of

Lectures
Molecular Magnetism and Magnetochemistry: T2-485-492
General Introduction: Magnetic Properties of the electron, Classification T3-Chapter 1 & 3
(Diamagnetism, Paramagnetism, Ferro, Antiferro- and Ferri-magnetism, Magnetic (Reference book R1
5 4+1
susceptibility (Temperature dependence, Superexchange) and class notes)
 Magnetism
• Very common in transition metal complexes → because of having partially filled metal d
or f orbitals
• Like electron spectroscopy, it provides additional and complementary information
• Magnetic properties depend on the Oxidation state, Electronic configuration (spin state)
and Coordination number of the central metal

Origin of Magnetic Properties

only moving charges
(currents) give rise to Electric Charge in Motion
magnetic fields. ↓ Magnetic Effect of Electric Current –
Magnetic Effects A magnetic field is a force field that is
created by magnetic dipoles and
moving electric charges, and it exerts
a force on other nearby moving
Nucleons Electrons charges and magnetic dipoles.
↓ ↓
Very weak Strong
Nuclear Magnetic Resonance (NMR) Influence the bulk magnetic
properties of substances
 Magnetic Properties of an Electron

Magnetic moments in an
electron arises due to its Orbital
and Spin angular Momentum

Magnetic Moment due to Orbital Motion

 Magnetic moment of a current loop,  = IA

I = current; A = area of the loop
 = (-ev/2pr) x pr2
r I = -e/T [T = orbital period] = -evrme/2me
The Orbital period as per Bohr's
me Postulates is given as T = 2πr / v, where  = -(e/2me)L
r is radius of the orbit, v is the velocity
of electron in that orbit. L = angular momentum = mvr
 Magnetic Moment due to Orbital & Spin Motion
L
𝒆 𝒆
= 𝜸𝒆 = 𝒈𝒚𝒓𝒐𝒎𝒂𝒈𝒏𝒆𝒕𝒊𝒄 𝒓𝒂𝒕𝒊𝒐
𝝁𝒍 = − 𝑳 𝟐𝒎 S
𝟐𝒎
𝒆 𝒉 Magnetic Moments due to orbital
𝝁𝒍 = − 𝒍(𝒍 + 𝟏) and spin angular momenta of an
𝟐𝒎 𝟐𝝅 electron are directed opposite to
the direction of the orbital (L) and
spin (S) angular momentum vector

𝒆
𝝁𝒔𝒑𝒊𝒏 = − 𝑺
𝟐𝒎
𝒆 𝒉
𝝁𝒔𝒑𝒊𝒏 = − 𝒔(𝒔 + 𝟏) Unit of Magnetism
𝟐𝒎 𝟐𝝅 𝒆
Experiments show that the spin 𝝁B = ħ Bohr
magnetic moment of the 𝟐𝒎 Magneton
electron is nearly twice this value 𝒆
𝒆 = 𝒉
𝟒𝝅𝒎
𝝁𝒔𝒑𝒊𝒏 = − 𝑺
𝒎 = 9.274 x 10-24 JT-1
 Gyromagnetic Ratio / Magnetogyric Ratio

For a classical rotating body: For a particle or system, γe is defined as the ratio of its
magnetic moment to its angular momentum → it is nothing
−𝒆 but a factor which converts angular momentum into
= 𝜸𝒆 = 𝒈𝒚𝒓𝒐𝒎𝒂𝒈𝒏𝒆𝒕𝒊𝒄 𝒓𝒂𝒕𝒊𝒐 magnetic moment
𝟐𝒎𝒆

An isolated electron has an angular momentum and a magnetic moment resulting from its
spin. While an electron's spin is sometimes visualized as a literal rotation about an axis, it
cannot be attributed to mass distributed identically to the charge.

The above classical relation does not hold, giving the wrong result by the absolute value of
the electron's g-factor, which is denoted ge:

−𝒆 𝒈𝒆𝝁𝑩
𝜸𝒆 = 𝒈𝒆 =
𝟐𝒎𝒆 ħ

ge = g-factor or Lande splitting factor of the free electron having value of 2.0023
Value differs appreciably for 2nd /3rd Row TMs and f-block elements
 Spin-Orbit Interaction → Theoretical vs Observed Moments
Paramagnetic moment originates due to the spins and orbital motions of the unpaired electrons
in the substance → Three possible modes of coupling: spin – spin, orbital – orbital, spin – orbital
Common in lanthanides

Theoretical magnetic moment for such a complex is given by:

μJ = μeff = g 𝑱(𝑱 + 𝟏)μb

J J+1 +S 𝑆+1 −𝐿(𝐿+1) Where J = total angular momentum quantum number

g=1+ L = total orbital angular momentum quantum number
2𝐽(𝐽+1) S = total spin angular momentum quantum number

If spin-orbit coupling is nonexistent or negligible:

μeff = μL+S = 𝟒𝑺 𝑺 + 𝟏 + 𝑳(𝑳 + 𝟏)μb

For 1st row transition metal complexes, the orbital contribution is effectively zero and can be
ignored and then the above equation reduces to :
μeff = μspin-only = 𝟒𝑺 𝑺 + 𝟏 μb
For an ion with n number
= 𝒏 𝒏 + 𝟐 μb of unpaired electrons
 Magnetic Properties (at 300 K) of some compounds of the lanthanide metals

μJ = μcalc = g 𝑱(𝑱 + 𝟏)μb

μcalc = μspin-only = 𝟒𝑺 𝑺 + 𝟏 μb
 Useful Magnetic Properties
Pole Strength:
The strength of a magnet may be expressed in terms of a unit pole. A unit pole may be defined as one that repels or attracts a
similar pole, places 1 cm away, with a force of 1 dyne.

Pole Strength and lines of force:

A magnetic field of unit intensity is taken to give a unit line of force per sq cm. If a pole of
strength m is enclosed in a sphere of radius 1 cm, a total of 4pm lines of force will emanate
from the pole, the surface area of the sphere being 4p cm2. This is Gauss’s law.

𝟒𝝅𝒎
The number of Lines of force/cm2 at the surface of the sphere is given by =𝒎
𝟒𝝅

Intensity of Magnetization:
The intensity of magnetization (I) induced in a body by an applied magnetic field is expressed in terms of the pole strength
induced per unit area (A), i.e., I = m/A → → → This is the situation of a hypothetical monopole

For a magnetic dipole of length l and pole area A, we can write

(𝑚 𝑥 𝑙) 𝑀𝑎𝑔𝑛𝑒𝑡𝑖𝑐 𝑚𝑜𝑚𝑒𝑛𝑡
I= =
(𝐴 𝑥 𝑙) 𝑣𝑜𝑙𝑢𝑚𝑒
 Useful Magnetic Properties
Magnetic Induction:
When a body is subjected to a magnetic field of strength H (i.e., H lines of force acting per unit area), the total lines of force
coming out per unit area of the body is given by the sum of H and an additional field DH due to the induced magnetization.
Since I represents the pole strength induced per unit area, we can write

B (magnetic induction) = H + DH = H + 4pI

DH will be negative (B < H) for diamagnetic and DH will be positive (B > H) for paramagnetic substance
Magnetic Permeability:
Magnetic permeability is the ratio of the density of lines of force within a body and that under vacuum
P (magnetic permeability) = B/H= 1 + 4p (I/H)
Magnetic Susceptibility:
The ratio (I/H) is the magnetic moment per unit volume per unit magnetic field and is known as the volume magnetic
susceptibility (k) of the body
k = I/H
Conceptually, k is treated as the response of a substance to induced magnetization

Gram Susceptibility: Molar Susceptibility:

χg = k/ρ ρ=density χM = χg x M M=Molecular weight of the substance
χg = χv /ρ
 Magnetic Moment
H
Magnetic moment is a more convenient property in
magnetochemistry compared to magnetic susceptibility +mH

In this figure, SN is a magnetic dipole of length l, pole strength m and P N

H is the strength of the applied magnetic field.
l
Turning moment of the couple = force x distance
= mH x PN θ
= mH x lsinθ
= mlHsinθ S
= Hsinθ -mH

When θ = 90◦
Turning moment of the couple = H → it is a measure of the work done by the magnetic field in rotating the
magnetic dipole by 90◦ i.e., from a position perpendicular to H to one parallel to H.

Magnetic susceptibility is determined experimentally and finally

converted to Magnetic moment using Curie equation (vide infra)
 Classification of Magnetic Properties

Diamagnetism Paramagnetism Ferromagnetism Antiferromagnetism Ferrimagnetism

 Diamagnetism

Properties:
• Repelled by magnetic field (closed shell electronic configuration)
• In closed shells, the spin and orbital moments of individual electrons balance each other,
leaving no net magnetic moment
• Magnetic moment induced in an external magnetic field → induced moment is proportional
to the strength of the field and will oppose the parent field.
• Independent of temperature and Permeability is less than (P<1) for diamagnetic substances

Examples: Copper, Zinc, Bismuth, Silver, Gold, Antimony, Marble, Water, Glass, Hg, alcohol, air,
H2, Ar etc.
 Paramagnetism

Properties:
• Attracted in a magnetic field with a force proportional to the product of field strength and
field gradient (a variation in the magnetic field across space).
• Substances allow more lines of force to pass through it
• Under the influence of a strong magnetic field, its position is parallel to the field → aligns with
the field
• Depends on temperature (inversely proportional) and Permeability is greater than (P>1) for
paramagnetic substances
• Paramagnetic substances can be treated as a micromagnet/small bar magnet where its north
pole will face the south pole of the applied magnetic field and vice-versa.
Examples: Tungsten, Caesium, Aluminium, Manganese, alkali and alkaline earth metals (Lithium,
Magnesium, sodium), Platinum, O2 etc.
 Ferro- vs Antiferro-magnetism
Magnetically Diluted System Magnetically Concentrated System

Individual paramagnetic centres in a Individual paramagnetic centres in a

substance are significantly apart → substance are sufficiently close → allows
practically no further interaction further magnetic interaction between
between neighbouring centres e.g., neighbouring centres e.g., Cu2(OAc)4,
[Ni(H2O)6]+2 and most of the 2H2O, Mn2(CO)10
coordination complexes

Ferromagnetism is actually greatly Antiferromagnetism arises when the

enhanced paramagnetism due to close magnetic moments at neighboring
alignment of magnetic dipoles in the centres are aligned in opposite
same direction directions i.e., antiparallel below a
Permeability (P) >> 1 certain temperature
Curie Temperature: Transition from Para Neel Temperature: Transition from
to Ferro-magnetism Para to AntiFerro-magnetism
Examples: Fe, Co, Ni, metallic alloys etc. Examples: Hematite, FeMn, MnO etc.
 Temperature Dependence of Magnetic Susceptibility

CrO2 is Metallic lattice of

ferromagnetic Fe is
below 386 K (TC) ferromagnetic
MnO is upto 768 0C (TC)
antiferromagnetic
below 118 K (TN)
 Relevance in Bioinorganic Chemistry

PNAS USA, 2015, 112, 13123

92 pm→ ←75 pm

↑42 pm
˂Fe–O–O
~115-130°
Deoxyhemoglobin
d6 : t2g4 eg2 Oxyhemoglobin (t2g6 eg0)

exp = 5.46 BM exp < 1 BM Sci Rep 10, 8569 (2020).

https://doi.org/10.1038/s41598-020-64364-y
Paramagnetic Antiferromagnetic
coupling
 Ferrimagnetism
Properties:
• Individual magnetic moments are systematically aligned so as to oppose others but giving rise
to some finite resultant magnetic moment e.g., Fe3O4 (inverse spinel)
• Below TC, spins are aligned antiparallel but do not cancel each other
• Half of the Fe(III) occupying tetrahedral sites and the Fe(II) with other half of Fe(III) occupying
octahedral sites.

• Magnetic moment of Oct sites are aligned in a direction opposite to the Tet sites
• Net effect is due to the Fe(II) species only.
 Superexchange
• Involves coupling of magnetic dipoles through electrons of intervening ligands
• Superexchange, or Kramers–Anderson superexchange, is the strong antiferromagnetic
coupling between two next-to-nearest neighbour cations through a non-magnetic anion. In
this way, it differs from direct exchange, in which there is coupling between nearest neighbor
cations not involving an intermediary anion.
• MnO provides a good example of superexchange (d5 system with configuration t2g3eg2)
• eg orbitals of Mn can overlap with the p-orbitals of oxygen along each of the cell axes.

- +
+ + + - - -
- +

dx2-y2 pz dx2-y2
 Temperature Dependence of Paramagnetism
• Pierre Curie studied the paramagnetic molar susceptibilities of various substances at different
temperatures and obtained a general relationship (in 1895):

𝑪
χM = known as Curie’s Law
𝑻
𝑁2𝜇2 𝑁𝜇2
• T = absolute temperature; C = Curie Constant (characteristic of the substance) = =
3𝑅 3𝑘

Curie Law is obeyed fairly well by paramagnetic

substances that are magnetically dilute →
paramagnetic centres are well separated from each other by
diamagnetic atoms

Materials that are not magnetically dilute, unpaired spins

on neighboring atoms may couple with each other
(Magnetic Exchange)
 Temperature Dependence of Paramagnetism
• Material that display exchange behavior can be treated with a modification of Curie’s Law

𝑪
χM = known as Curie – Weiss Law
(𝑻−𝜽)
• T = absolute temperature; θ = Weiss Constant (unit of Temp) = a temp at which the straight line
(1/χM vs T) cuts the T-axis
Curie-Weiss Law for
Antiferromagnetic
Substance (TN)

Curie Law

Curie-Weiss Law for

Ferromagnetic Substance (TC)
 Temperature Dependence of Paramagnetism
• The applied field induces a magnetic moment proportional to the magnetizability of the
molecule which allows the Curie’s law to be written as:

𝝁𝟐
χM = N(ξ + ) where ξ = magnetizability
𝟑𝒌𝑻
𝑪
χM = A + where A = Nξ and C = N2/3k
𝑻

N𝝁𝟐
• For many practical purposes, it is convenient to neglect ξ and write: χM =
𝟑𝒌𝑻

𝟑𝒌 Derived assuming that the individual

 = 𝝌𝑴𝑻 dipoles are completely independent
Relationship between 𝑵
Magnetic Moment and
Magnetic Molar Orientations of dipoles is influenced by the
𝟑𝒌
Susceptibility  == 𝝌𝑴(𝑻 − 𝜽 orientation of other neighboring dipoles →
leading to Inter-dipole interaction
𝑵
 Validity of Curie/Curie-Weiss Law

Curie Law Curie-Weiss Law

Exhibited only when: Curie Law will not be obeyed if:

(1) the magnetic susceptibility arises entirely (1) there are some cooperative interaction
from the ground state and there are no between the neighboring magnetic dipoles
thermally accessible state (2) there are energy levels whose population
(2) the magnetic dipoles are completely changes with changing temperature or
independent of each other (3) the applied magnetic field induces some
Ideal Curie magnets are chrome alum temperature-independent paramagnetism
[KCr(SO4)2.12H2O, (NH4)2Mn(SO4)2.6H2O] and Weiss constant (θ) takes care of the
Gd2(SO4)3.8H2O cooperative interaction
θ = -ve for antiferromagnet
θ = +ve for ferromagnet
 Temperature Independent Paramagnetism (TIP)

Properties:
• Weak Paramagnetic behavior independent of T (substances may or may not have unpaired e-)
• Does not originate from any permanent magnetic dipole
• This paramagnetism is induced when the substance is placed in a magnetic field which can
affect a change in the ground state of the atom/ion
• Mixing up of higher energy excited states with the ground state and stimulation of current
through movement of e- to LUMO and (LUMO + n) orbitals (n =1, 2, 3,….)
• Also known as orbital paramagnetism where the influence of thermal agitation on their
alignment does not exist
• Systems with low-lying excited states show such TIP.
Examples: chromate (CrO4-2) and permanganate (MnO4-) ions (d0 configuration)