Tetragonal distortion from octahedral symmetry

ML6 (Oh ) MX 2 L4

Cis(C2v )

Trans( D4 h )

Reduction of symmetry: consequences

How a Term of Oh symmetry splits when the symmetry decreases, is given in

the following correlation table.

Tetragonal distortion from octahedral symmetry

Tetragonal distortion from octahedral symmetry in ML6 type complex ??

Jahn - Teller Distortion

Jahn-Teller theorem: For a nonlinear molecule in an electronically degenerate state,
distortion must occur to lower the symmetry, remove the degeneracy, and lower the
energy.

No J-T distortion:
d3, d5(HS), d6(LS), d8

Degeneracy of orbitals & Terms

Jahn - Teller Distortion: Orbital picture

J-T gives NO information:

-Magnitude of splitting
- whether elongation or
compression?

Jahn - Teller Distortion: Examples

Example: d1 system, [TiCl6]3-

A1g
B1g
Eg
B2g

Pronounced Jahn - Teller Distortion

Dynamic J-T:
Elongated:
Undisturbed:
Compressed:

Jahn - Teller Distortion in Chelated compounds

(Conflict b/w stabilization from chelate & J-T distortion)

CHARGE TRANSFER TRANSITION

CT transition do not involve the complete transfer of one electron from one atom to
another; rather in a molecular orbital sense, they represent the transition of an
electron from a MO primarily located on one atom, to a MO primarily located in
another atom.

Classifications:
1) Transition b/w levels primarily located on the metal, e.g. d d transition
2) Transition
ligands, e.g. * transition
3) Transition b/w levels of metal-to-ligand or vice versa (CT Transition)
MLCT, LMCT, LLCT, MMCT
Charge Transfer transition may be regarded as an internal redox process, which
makes it possible to use the concept of HOMO and LUMO
Koopmans Theorm (Frozen orbital): IP = - HOMO energy, EA = - LUMO energy
Atoms/ions with Low IP
- Readily oxidisable
- Filled orbitals of relative high energy

Atoms/ions with High EA

- Readily reducible
- Low laying empty orbitals

Ideal combination for CT Transition: Metals with high IP & Ligands with High EA
(minimum gap b/w HOMO of metal & LUMO of ligands)
Note: If the gap is too small ( < 10000 cm-1), complete electron transfer may occur with
oxidation of metal and reduction of ligands, resulting break down of the complex, e.g.
Co(H2O)6]3+, FeI3

Charge Transfer Spectra in TM cpmplexes

Ideal Conditions:
Low IP of metal (readily oxidizable);

High EA of ligand (readily reducible)

To see transition in visible range: oxidizable Ligands + reducible metal

Ligand-to-Metal Charge Transfer Spectra

Metal-Ligand combination:
Metal with high IE, low energy empty orbitals
e.g. transition metal with high oxidtion state
Ligand with low EA, high energy filled orbitals
e.g. chalcogens/heavy halides

For MnO4-

Increase in energy of CT band

(easy of oxidation)
Iodide < Bromide < Chlodide < Floride
- Presence of electron donating ligand: lower
- More reducible the metal (M-L ionic bond):
Lower
- Independent of oxidation state of metal
(M-L covalent)
- Increases with coordination no.

Metal-to-Ligand Charge Transfer Spectra

Metal-Ligand combination:
Ligands with low energy empty orbitals
e.g. Pi* orbital: CO, pyridine, pyrazine
Occupied metal centered filled orbitals

MAGNETIC PROPERTIES OF COMPLEXES

Depends on:
Oxidation state of metal
Electron configuration
Coordination number of metal

MATERIAL IN A MAGNETIC FIELD

(a) Diamagnetic material:
in the presence of a field, dipoles are induced and
aligned opposite to the field direction.

Diamagnetic materials tend

to repel flux lines weakly,
Examples: water, protein, fat

(b) Paramagnetic material:

Diamagnetism is a universal property.
Paramagnetism is much larger than diamagnetism
and decreases with temperature.

magnetic materials tend to

concentrate flux lines.
Examples: iron, cobalt

MATERIAL IN A MAGNETIC FIELD

The response of a material to a Magnetic Field H is called Magnetic
Induction B
The relationship between B and H is a property of the material
In some materials and in free space B is a linear function of H but in
general it is much more complicated and sometimes it is not even
single valued

H B H 0

4 I

B [Tesla] I Intensity of Magnetization

B / H 0 1 4I / H 0 4
I / H 0 Magnetic Susceptibility per unit volume

Specific (mass) Susceptibility

d Density of material
Molar Susceptibi lity M .MW

ORIGIN OF MAGNETISM IN A MATERIAL

A moving electric charge, macroscopically or microscopically is
responsible for Magnetism

Origin of Magnetism

Nuclear spin

Weak effect

Spin of electrons

Unpaired electrons required

for net Magnetic Moment

Orbital motion of electrons

Magnetic Moment resultant from the spin of a single unpaired electron

Bohr Magneton = 9.273 x 1024 A/m2

Magnetic Moment Measurement

By a magnetic balance.
If a substance has unpaired electrons, it is paramagnetic,
and attracted to a magnetic field.

(a) Magnet (of field H) off

(b) Paramagnetic (HB > H)
(c) Diamagnetic (HB < H)

r 1.644 10 cm mol
5

for Hg[Co( SCN ) 4 ]

Sample size:
Gives:

Faraday Method
mg
molar sus. ()

Gouy Method

g
Volume sus. ()

f
fr

m mr r

Magnetic moment of complexes: Theory

N
M
3RT
2

Theory

3RT M

2.84 T M
2
N

Magnetic moment incorporating all the three types of coupling, viz., spin-spin,
orbital- orbital, and spin-orbital:

is the magnetic moment, J is the total angular momentum quantum number and
g is the Land splitting factor for the electron, L is the orbital-angular momentum
and S is the spin-angular momentum.
When the spin-orbit coupling is negligible or absent:
(spin-orbit)
When orbital contribution is negligible or absent:
Substituting, S = n/2, where n is the number of unpaired electrons, gives
Spin-only value:

Magnetic properties of Ln-complexes

Magnetic properties of 1st-Row TM complexes

Calculated values are spin-only

Co-existance of different spin states

Many transition metal ions are able to form high-spin and low-spin complexes
depending up on the strength of the ligand field. When the ligand is of
intermediate field strength, both high-spin and low-spin complexes can coexist
in equilibrium.

Example: Fe2+ (d6) system

[Fe(H2O)6]2+ ( - P < 0), S = 2
[Fe(CN)6]4+ ( - P > 0), S = 0

P kT

Variation in magnetic moment of [Fe(Phen)2(NCS)2]

Temperature Dependence
For magnetically dilute paramagnetic substances

Materials that are not magnetically dilute gives magnetic exchange.

TC: Curie Temperature, TN: Neel Temperature

Comparison of magnetic behavior

Spin-alignment
(below Tc & TN )
vs.
spin-randomness
(above Tc & TN )