Universidad del Valle

Inorganic Chemistry II

Prof. Renso Visbal Acevedo Departamento Química

email: [email protected]
 Electronic Spectroscopy and Magnetism
Transition Metal Complexes

Mixed valence [CoFe] complexes and

cyanide-bridged discrete molecules
HOT TOPIC exhibit photoinduced switching
between antiferromagnetic and
ferromagnetic phases.

When the complex was irradiated (λ =

808 nm) with the temperature set at 5
K, a rapid increase of χmT values was
observed after ten hours of
[Co(II)((R)-pabn)] [Fe(III)(tp)(CN)3](BF4)•MeOH•2Hirradiation.
2O
Taken from Nature Chemistry, 2012, 4, 921-926
 Electronic Spectroscopy and Magnetism
Transition Metal Complexes

Light-Induced Spin Change by Photodissociable External

Ligands: A New Principle for Magnetic Switching of Molecules

HOT TOPIC

Published in: J. Am. Chem. Soc.  2011, 133,

16243-16250.
Copyright © 2011 American Chemical Society
 Crystal Field Theory of
Transition Metal Complexes
Crystal Field Theory

Molecular Orbital Theory is the most complete theory use for the
understanding of the vast majority of chemical and physical properties
observed in simple and complex molecules. So, Why Crystal Field Theory
is so important?

The complexes behave as if the bonding between the central metal ion
and the surrounding ligands is purely electrostatic.
z

+
M

x y
Octahedral Complexes A metal s orbital in an octahedral complex
 Crystal Field Theory of
Transition Metal Complexes

A set of metal p orbitals in an octahedral crystal field

The dxy, dyz and dzx metal orbitals in an octahedral crystal field
 Crystal Field Theory of
Transition Metal Complexes

The dx2-y2 and dz2 orbitals in an octahedral crystal field

Although they look very different, the fact that they can be mixed by an axis
relabelling shows that they are a degenerate pair
 Crystal Field Theory of
Transition Metal Complexes

T1u T2u

In an octahedral crystal field the f orbitals of a metal atom

split into two sets which are triply degenerate and one orbital
which is singly degenerate
 Crystal Field Theory of
Transition Metal Complexes

A2u

In an octahedral crystal field the f orbitals of a metal atom

split into two sets which are triply degenerate and one orbital
which is singly degenerate
 Crystal Field Theory of
Transition Metal Complexes

The more stable set is that in which

an electron experiences least
The combined repulsive and splitting repulsion “destabilization” from the
effect of an octahedral crystal field on electrons on the ligands.
the energies of a set of metal d
orbitals This set is that composed of dxy, dyz
and dzx because this set keeps the d
electrons away from the ligand
electrons.
 Crystal Field Theory of
Transition Metal Complexes
d x2-y2, d z2 (eg)
Δ value for metals of the
3Δ first raw:
5 M+: 10.000 cm-1
Δ M2+: 5.000-15.000 cm-1
M3+: 10.000-30.000 cm-1
-2 Δ
5
This value is up to twice for
dxy, dyz, dzx (t2g) second or third raw complex
The d orbital splitting in an octahedral crystal field

The vast majority of experimental data on transition metal complexes gives

information on the splitting between the d orbitals but not on their absolute
displacements from the free ion energy

Spectrochemical Series
I-, Br-, SCN- (S-bonded) < Cl- < F- < OH- < H2O < SCN- (N-bonded) <
NH3 = py < SO3- < bpy < NO2- (N-bonded) < CN-

MnII < NiII < CoII < FeII <VII <FeIII < CrIII < VIII < CoIII < MnIV < RhIII < PdIV <
IrIII < PtIV
 Crystal Field Theory of
Transition Metal Complexes
M and LI values for octahedral complexes

These two series can be

brought together for octahedral
complexes, including those
which contain a mixture of
ligands:

Δ = M  Σ  nILI x 103

Here M and LI are taken from
the table and nI is the number
of ligands of type I associated
with LI in the complex (for
genuine octahedral complexes
nI = 6)
 Crystal Field Theory of
Transition Metal Complexes
[Fe(H2O)6]2+
Small Δ
d6 High spin

d4 d5 d6 d7 Pale blue
High spin

d1 d2 d3 d8 d9

[Fe(CN)6]4-
Large Δ
d6 Low spin

d4 d5 d6 d7
Yellow
Low spin

The high spin (small Δ) and low spin (large Δ) possibilities for d4-d7 octahedral
complexes
 Square planar complexes

There are two conceptually different

approaches to square planar
complexes. One may regard the d
orbital splitting as being that obtained
when two trans ligands are
simultaneously removed from an
octahedral complex.

Alternatively, one may use the same

approach as that used for octahedral
The usual choice of coordinate and tetrahedral complexes and
axes in a square planar complex consider the splitting of the free ion d
orbitals by a square planar ligand
field.
 Square planar complexes

Since, in a square planar

complex, x ≡ y ( ≡ z)
with the ligands in the
xy plane, the dzx and dyz
orbitals will be more
stable than dxy leading
to the qualitative d
orbital splitting pattern
shown in the figure.

The centre of gravity of

the split energy levels
no longer coincides with
the free-ion level.

Correlation of the d orbital splitting in a square planar

ligand field with those in an octahedral ligand field
 Square planar complexes

Note that whilst Δ may be

regarded as the energy
difference between the
centres of gravity of the
upper pair and lower trio of
levels for octahedral
complexes, two additional
splitting energies are
needed to give a complete
specification of the energy
level diagram for square
planar complexes.

These are the splittings of

the b1g-a1g orbitals and of
Modified correlation between octahedral and the b2g-eg.
square planar crystal field splittings
 Electronic Spectroscopy and Magnetism
Transition Metal Complexes
Magnetic properties of transition metal complexes

Published in: J. Am. Chem. Soc.  2011, 133, 16243-16250.

Copyright © 2011 American Chemical Society
 Electronic Spectroscopy and Magnetism
Transition Metal Complexes
Magnetic properties of transition metal complexes

Published in: J. Am. Chem. Soc.  2011, 133, 16243-16250.

Copyright © 2011 American Chemical Society
 Electronic Spectroscopy and Magnetism
Transition Metal Complexes
Magnetic properties of transition metal complexes

Crystal structure of the

paramagnetic material

Published in: J. Am. Chem. Soc.  2011, 133, 16243-16250.

Copyright © 2011 American Chemical Society
 Electronic Spectroscopy and Magnetism
Transition Metal Complexes
Magnetic properties of transition metal complexes
F F
F F
F F
R
F F N
R N
N 365 nm N
F F N
N R
455 nm N
N Ni N R
N N
F N F

F F
F F
F F
F F
b1g

eg
a1g

d8 b2g

In this case, this t2g

phenomenin is dominated eg
Octahedral Square planar
by the steric hindrance Paragmagnetic Diagmagnetic
 Weak Field Complexes

➢ Weak field complexes are those for which the crystal splitting Δ, is
smaller than the electron-repulsion and -exchange energies.

➢ The most important is the attraction between an electron and the

nucleus. Next, the effects of interelectron repulsion (this includes the
exchange energy) are considered, then the coupling between the spin
and orbital motion of the electron (spin-orbit coupling) and so on.

➢ The most stable electron arrangement in the free ion, which will be
preserved in weak field complexes, is one in which electron-electron
repulsion is a minimum.

➢ The electrons are as far apart as is possible. This will be when they
occupy different orbitals as much as is possible and this, in turn,
means that the term of highest spatial (orbital) and spin multiplicity
will be the ground state.
 Spectroscopic Terms

➢ the symbols A1g, A2g, Eg, T1g and T2g will be encountered with a spin state
designated, for example, 2Eg ('doublet ee gee') and 3T1g.

2
➢ We shall refer to 𝑡2𝑔, ('tee two gee two'), for example when talking about
two electrons in a set of t2g orbitals (other books may refer to this as
3
(t2g)2). Symbols such as 𝑡2𝑔 or (t2g)3 indicate that the set of three orbitals
labelled t2g are occupied by three electrons.

➢ We talk of 'the P term arising from the p1 configuration', or 'the P term

arising from the d2 configuration' and so on.
 Spectroscopic Terms

The spectrum of the d3 complex [Cr(NH3)6]3+

 Spectroscopic Terms

The electronic configuration is an incomplete description of the

arrangement of electrons in atoms

In the configuration 2p2:

1. The two electrons might occupy orbitals with different orientations
(ml = 1, 0, -1)

2. the designation 2p2 tells us nothing about the spin orientations of

the two electrons ms = +1/2 or –1/2

The different ways in which the electrons can occupy the

orbitals specified in the configuration are called the
microstates of the configuration
Both electrons occupy an orbital with ml = +1, but
(1+, 1-)
do so with opposite spins
2p2
Both electrons have ms = +1/2 but one occupies
(-1+, 0+) the 2p orbital with ml = -1 and the other occupies
the orbital with ml = 0
 Spectroscopic Terms

If electron-electron repulsions are taken into account, we obtain

the spectroscopically distinguishable energy levels called terms

For light atoms (3d configurations) the order of importance is S > L.

For heavy atoms, the spin and orbital angular momenta of individual
electrons are strongly coupled together by spin-orbit coupling (J = total
angular moment).

Russel-Saunders Coupling
The process of combining electron angular momenta by summing first
the spins, then the orbital momenta, and finally combining the two
resultants is called Russell-Saunders coupling

The coupling scheme most appropriate to heavy atoms (that is, atoms of
the 4d and 5d series of elements) is called jj-coupling
 Spectroscopic Terms

According to the Clebsch-Gordan series, the possible values of L

and S are
L = l1 + l2, l1 + l2 - 1, ... , |l1 - l2|

S = s1 + s2, s1 + s2 - 1, ... , |s1 - s2|

For example, an atom with configuration d2 (l1 = 2, l2 = 2)

can have the following values of L:
L = 2 + 2, 2 + 2 - 1, ... , |2 - 2| = 4, 3, 2, 1, 0

The total spin (because s1 = 1/2 , s2 = 1/2) can be

S = 1/2 + 1/2, 1/2 + 1/2 - 1, ... , |1/2 – 1/2| = 1, 0
 Spectroscopic Terms

Once L and S have been found, we can write down the

allowed values of the quantum numbers ML and MS,

ML = L, L - 1, ... , -L (2L + 1 values of ML)

MS = S, S - 1, ... , -S (2S + 1 values of Ms)

If one electron has the quantum number ml1 and the

other has ml2, then ML = ml1 + ml2

Similarly, MS = ms1 + ms2

(0+, -1- ) is a microstate with ML = 0 -1 = -1 and MS = 1/2 +(-1/2) = 0

 Spectroscopic Terms

By analogy with the notation s, p, d, ... for orbitals with l =

0, 1, 2,..., the total orbital angular momentum of an
atomic term is denoted by the equivalent uppercase letter:

L=0 1 2 3 4…

S P D F G … then alphabetical (omitting J)

The total spin is normally reported as the value of 2S + 1,

which is called the multiplicity of the term:

S=0 1/2 1 3/2 2 L=1

2S + 1 = 1 2 3 4 5 3P

S=1
singlet doublet triplet
Spectroscopic Terms

For light metals (3d)

For heavy metals (4d and 5d)

J = (L + S), (L + S - 1) ... |L - S|
 Spectroscopic Terms

For light metals (3d)

For heavy metals (4d and 5d)

J = (L + S), (L + S - 1) ... |L - S| MJ = J, J-1 … -(J-1), -J

 Spectroscopic Terms

Determining the number of microstates

 Spectroscopic Terms

Determining the number of microstates

For Hydrogen (Z = 1): 1s1

The complet spectroscopic term: 2S1/2

 Spectroscopic Terms

Determining the number of microstates

For Boron (Z = 5): 1s22s22p1

L = 1 (a P term)

S = 1/2: (2S+1)=2 (doublet)

J = (L+S), (L+S-1) = 3/2, 1/2

Spectroscopic
terms: 2P3/2 or 2P1/2
 Spectroscopic Terms

What about de relative energy of the terms

Relative energy

3F < 1D 3F < 3P

S=1 S=0 L=3 L=1

 Spectroscopic Terms

What about de relative energy of the terms

Relative energy
C: 1s2 2s2 2p2 O: 1s2 2s2 2p4
3P0 < 3P1 3P1 < 3P0

S=1 S=1 S=1 L=1

L=1 L=1 L=1 L=1
J=0 J=1 J=1 J=0
 Spectroscopic Terms

What about de relative energy of the terms

For Boron (Z = 5): 1s22s22p1

Spectroscopic
terms: 2P3/2 or 2P1/2

For the p1 configuration, the p level is less than half-filled, and

therefore the ground state level is the one with the lower value
of J, i.e. 2P1/2.
 Spectroscopic Terms

Determining the number of microstates

For Carbon (Z = 6): 1s22s22p2

Spectroscopic terms:

1D
2

➢ The energy ordering is

3P < 3P < 3P < 1D < 1S
0 1 2 2 0
➢ The ground state is the 3P0 term
3P , 3P , 3P
2 1 0

1S
0
 Spectroscopic Terms

What about de relative energy of the terms

The spin multiplicity rule is fairly reliable for predicting the
ordering of terms, but the ‘greatest L’ rule is reliable only for
predicting the ground term, the term of lowest energy.

For example, for d 2 the rules

predict the order:

Relative Energy
3F < 3P < 1G < 1D < 1S

but the order observed

(experimentally) for Ti 2+ from
spectroscopy is

3F < 1D < 3P < 1G < 1S

 Spectroscopic Terms

Identifying the ground term of a configuration

Normally, all we want to know is the identity of the ground
term of an atom or ion.

1. Identify the microstate that has the highest value of MS.

2. Identify the highest permitted value of ML for that

multiplicity.
Example:
What is the ground term of the configurations
(a) 3d5 of Mn2+ and (b) 3d3 of Cr3+?
S = 5/2
Multiplicity = 6
d5 configuration 6S
ml = +2, +1, 0, -1, -2
ML = Σml = 0
L=0
 Spectroscopic Terms

Identifying the ground term of a configuration

Normally, all we want to know is the identity of the ground
term of an atom or ion.

1. Identify the microstate that has the highest value of MS.

2. Identify the highest permitted value of ML for that

multiplicity.
Example:
What is the ground term of the configurations
(a) 3d5 of Mn2+ and (b) 3d3 of Cr3+?
S = 3/2
Multiplicity = 4
d3 configuration 4F
ml = +2, +1, 0
ML = Σml = 3
L=3
 Spectroscopic Terms

➢ A crucial factor turns out to be the number of unpaired

electrons, n, associated with each term and this is
indicated by the number (n + 1) as a superscript thus: 2P,
3D and so on.

➢ An F term splits up into either T1u, T2u and A2u or T1g, T2g
and A2g subsets. Which of these is correct is determined
by the g or u nature of the configuration from which the F
term is derived.

➢ Because f orbitals are u in character the 2F term

corresponding to an f1 configuration splits up into 2T1u,
2T
2u and A2u components. Similarly, the F term derived
2 3

from the d2 configuration splits into 3T1g, 3T2g and 3A2g

components because the d orbitals are g in character.
 Weak Field Complexes

Crystal field components of the ground and some excited terms

of dn (n = 1-9) configurations
 Weak Field Complexes

d1 configuration
2D
Ground term Excited term
term 2T 2E
2g g

We speak about
electrons

(a) Ground and (b) excited states derived from the d1 configuration in an
octahedral crystal field

1
As a d1 configuration gives rise to a 2D term, the 𝑡2𝑔 configuration gives rise to
a 2T2g term. Similarly, the (excited) 𝑒𝑔1 configuration gives rise to a 2Eg term.

We conclude that the 2T2g term is the more stable because it means that the
solitary d electron is in the t2g orbitals.
 Weak Field Complexes

d4 configuration
Ground term Excited term
5D 5E 5T
term g 2g

We speak about holes

(a) Ground and (b) an excited state with the same spin multiplicity, derived
from the d4 configuration in an octahedral crystal field.

The most stable situation is that in which the hole is in the eg orbitals. The
ground term is therefore 5Eg.

In the d4 case, therefore, the splitting of the Eg and T2g levels is the inverse
of that in the d1 case.
 Weak Field Complexes

d6 configuration
Ground term Excited term
5D 5T 5E
term 2g g

We speak about
electrons

(a) Ground and (b) lowest excited state of the same spin multiplicity, derived
from the d6 configuration in an octahedral crystal field.

It differs from spherical symmetry by the presence of a single electron,

which is more stable when it is in the t2g orbitals.

The splitting therefore follows the d1 case, the 5T2g term being more stable
than the 5Eg term by an energy Δ.
 Weak Field Complexes

d9 configuration
Ground term Excited term
2E 2T
2D term g 2g

We speak about holes

(a) Ground and (b) excited state derived from the d9 configuration in an
octahedral crystal field.

The 2D term arising from the d9 configuration differs from spherical

symmetry by the presence of a hole in the eg orbitals in the ground state.

The ground state is therefore of 2Eg symmetry and the excited state, at an
energy of Δ above, is of 2T2g symmetry.
 Weak Field Complexes

d2 configuration
3F
Ground term Excited term Excited term
term 3T 3T 3A
1g 2g 2g
We speak about
electrons

(a) Ground and (b, c) two excited state configurations of a d2 ion in an

octahedral crystal field.

In the ground term derived from the 3F term of the d2 configuration

we will find that there are two electrons in the t2g orbitals.
 Weak Field Complexes

d3 configuration
4F term Ground term Excited term Excited term
4A 4T 4T
2g 2g 1g
We speak about
holes

(a) Ground and (b, c) two excited state configurations of a d3 ion in an

octahedral crystal field.

In the ground term derived from the 4F term of the d3 configuration

we will find that there are two holes in the eg orbitals.
 Weak Field Complexes

d7 configuration
Ground term Excited term Excited term
4F term 4T 4T 4A
1g 2g 2g

We speak about
electrons

(a) Ground and (b, c) two excited state configurations of a d7 ion in

an octahedral crystal field.

The 4F term derived from the d7 configuration gives rise to an excited 4T2g
and 4A2g terms, with two holes occupying the t2g orbitals
 Weak Field Complexes

The 3F term derived from the d8 configuration gives rise to an excited 3T1g
term, two holes occupying the t2g orbitals

d8 configuration
Ground term Excited term Excited term
3F term 3A 3T 3T
2g 2g 1g

We speak about
holes

(a) Ground and (b, c) two excited state configurations of a d8 ion in an

octahedral crystal field.
 Weak Field Complexes

d5 configuration 6S term

The 6S ground state, which is derived from d5 configuration, is orbitally non-

degenerate and so no crystal field splitting can occur. The behavior of this 6S
term parallels that of an s orbital and becomes 6A1g in an octahedral crystal
field

The splitting of the weak field dn (n = 1-9) ground state terms in an

octahedral crystal field
Weak Field Complexes

The splitting of the weak field dn (n = 1-9)

ground state terms in an octahedral crystal field
 Electronic Spectra

The broadness is a consequence of the

Franck–Condon approximation which
states that electronic transitions are very
much faster than nuclear motion

400 nm 25 000 cm-1

200 nm 50 000 cm-1

Absorptions arise from transitions

between electronic energy levels:
 Electronic Spectroscopy in
Transition Metal Complexes
Selection Rules
Electronic transitions between energy levels obey the following
selection rules:

Spin allowed
2Eg 2T2g
3T2 3E

Spin forbidden
4T2g 6A1g
1Eg 3A2g

Laporte allowed
s p
p d

Laporte forbidden
s s
p p
 Electronic Spectroscopy in
Transition Metal Complexes
Selection Rules

Typical ϵmax values for electronic absorptions; a large ϵmax corresponds to

an intense absorption and, if the absorption is in the visible region, a
highly coloured complex

Since these selection rules must be

strictly obeyed, why do many d-block
metal complexes exhibit ‘d–d’ bands in
their electronic spectra?
 Electronic Spectroscopy in
Transition Metal Complexes
Selection Rules

A spin-forbidden transition
becomes ‘allowed’ if, for
example, a singlet state mixes to
some extent with a triplet state:
spin orbit coupling (SOC):
3d < 4d, 5d elements
Spin-allowed ‘d–d’ transitions Mixing of d and p orbitals can
remain Laporte-forbidden and occur because of the
temporary lost of symmetry
their observation is explained as a consequence of
by a mechanism called molecular vibration (10-13 s)
‘vibronic coupling’
 Electronic Spectroscopy in
Transition Metal Complexes
Selection Rules

Exercise

Explain why an electronic transition for high-spin

[Mn(OH2)6]2+ is spin-forbidden, but for [Co(OH2)6]2+ is
spin-allowed
 Electronic Spectroscopy in
Transition Metal Complexes
Charge-transfer spectra
If the absorption of light causes an electronic transition within an atom or
molecule, therefore there is a movement of charge density.

Many transition metal complexes exhibit strong charge-transfer absorptions

in the UV or visible range.

These are much more intense than d!d transitions, with ϵ between
1,000-50,000 M-1cm-1 (as compared to 10 M-1cm-1 for d!d transitions).
 Electronic Spectroscopy in
Transition Metal Complexes
Charge-transfer spectra
In metal complexes, intense absorptions (typically in the UV or visible part
of the electronic spectrum) may arise from ligand-centred n–π︎* or π ︎ –π︎*
transitions, or from the transfer of electronic charge between ligand and
metal orbitals.

The latter fall into two categories:

 Electronic Spectroscopy in
Transition Metal Complexes
Ligand to Metal Charge Transfer
Transitions in the MnO4- ion
 Electronic Spectroscopy in
Transition Metal Complexes

Ligand to Metal Charge Transfer Bands

The following series of complexes illustrate the effects of the metal, ligand
and oxidation state of the metal on the position (︎λmax) of the LMCT band
metal centre
becomes harder
to reduce
the ligand becomes easier to oxidize
the metal becomes easier to reduce
 Electronic Spectroscopy in
Transition Metal Complexes
Ligand to Metal Charge-Transfer transitions (LMCT)
These are a common type of transitions, in which a ligand
electron is transferred to a metal orbital and the charge
separation within the complex thereby reduced.

The process can lead to a permanent transfer of charge or the

excited molecule can reached the ground state by different
relaxation modes.

R
Ph2
N P H Under
Au C
N P C UV light
R Ph2

M-NHC
complex

J. Am. Chem. Soc., 2013, 135, 4712.

 Electronic Spectroscopy in
Transition Metal Complexes
DFT and TDDFT calculations

R
Ph2
N P H
Au C
N P C
R Ph2

M-NHC
complex

Singlet Triplet

LML’CT

J. Am. Chem. Soc., 2013, 135, 4712.

 Electronic Spectroscopy in
Transition Metal Complexes
Metal to Ligand Charge-Transfer transitions (MLCT)
MLCT typically occurs in complexes with π acceptor ligands. The empty π*
orbitals on the ligands accept electrons from the metal upon absorption of
light. The result is oxidation of the metal.

Often, the associated

absorption occurs in the
UV region of the
spectrum, although
sometime they appear
in the visible region:

[Fe(bpy)3]2+ = 520 nm
[Ru(bpy)3]2+ = 452 nm

Absorption
of light
[Fe(CN)6]4- (d6) [Fe(CN)6]3- (d5)
 Electronic Spectroscopy in
Transition Metal Complexes
Intraligand transitions (IL)
These charge-transfer transitions are usually located in the ultraviolet region of
the spectrum, and are basically associated with the electron density movement
into the ligand itself.

Corresponding transitions occur in the coordinated ligand but can usually be

identified by comparison with the spectrum of the free ligand.
270 410 435 270 410
Excitation 435
Emission Excitation
Emission
460
Imidazolium

Intensity
Intensity

375
460 M-NHC
375 salt
complex

300 400 500 200 300 400 500

λ (nm) λ (nm)

R R F F
N N
H Au F
N N
F F

N N
 Electronic Spectroscopy in
Transition Metal Complexes
Intervalence Charge-Transfer (IVCT) Bands
These charge-transfer bands appears when there is an overlap between the
orbitals on the two or more metal atoms with different valence states.

This overlap involves both ground and excited electronic states. The intense
colors characteristic of these bands are mainly due to the large electric dipole
change as consequence of the movement of electron density from ground to
excited state between non-equivalent metal centers (mixed-valence).

LnM+-bridge-M'Ln + hν → LnM-bridge-M'+Ln

Photoinduced or thermally or activated

 Electronic Spectroscopy in
Transition Metal Complexes
Intervalence Charge-Transfer (IVCT) Bands

The IVCT band is usually observed in the Co(II) Fe(III)

visible or near  infrared region of the
spectrum and is broad Absorption
808 nm
of light

Fe(II) Co(II)

[Co(II)((R)-pabn)] [Fe(III)(tp)(CN)3](BF4)•MeOH•2H2O
Taken from Nature Chemistry, 2012, 4, 921-926
 Electronic Spectroscopy in
Transition Metal Complexes
Electronic spectra of octahedral and
tetrahedral complexes - d1 configuration
Electronic spectroscopy is a complicated topic and we shall restrict our
discussion to high-spin complexes. This corresponds to the weak field limit
(high spin)

[Ti(H2O)6]3+
2E
g ← 2T2g transition

The electronic spectrum consists

in two bands, rather than one,
which can be rationalized in terms
of a Jahn–Teller effect in the
excited state, t2g0eg1 Energy level diagram for a d1 ion in an
octahedral field
 Electronic Spectroscopy in
Transition Metal Complexes
Janh-Teller Effect

Any non-linear ion or molecule which is in an

orbitally degenerate term will distort to [Ti(H2O)6]3+
relieve this degeneracy. 2E
g ← 2T2g transition

All of the Eg, T1g and T2g terms of dn

configurations, in principle, are unstable with
respect to some distortion which reduces the
symmetry.

The Janh-Teller effect is of importance in

the spectra of octahedral transition metal
complexes because the transitions observed
usually involve the excitation of a single
electron from a t2g to an eg orbital.
-2

M M

-2
 Electronic Spectroscopy in
Transition Metal Complexes
Janh-Teller Effect
[Ti(H2O)6]3+
2E
g ← 2T2g transition

dz2 is more stable dx2-y2 is more stable

M M

2 long 4 long
4 short 2 short
More stable Less stable
 Electronic Spectroscopy in
Transition Metal Complexes
d9 configuration (e.g. Cu2+)

For the d9 configuration in an octahedral field, the ground state of the

free ion (2D) is again split into 2T2g and 2Eg terms, but, in contrast to the d1
ion, the 2Eg term is lower than the 2T2g term

600-700 nm

The color of the complex

is the sum of the light
not absorbed (reflected)
by the complex
 Electronic Spectroscopy in
Transition Metal Complexes
Orgel Diagrams
For a d9 ion in an octahedral field, the splitting diagram is an inversion of that
for the octahedral d1 ion. This relationship is shown the Orgel diagram, which
describes the octahedral d1 (right-hand) and d9 cases (left-hand)

Only one electronic transition

from a ground to excited state is
possible:

• for octahedral d1 and d6, the

transition is Eg ← T2g


• for octahedral d 4 and d 9, the

transition is T2g ← Eg

• for tetrahedral d1 and d6, the

transition is T2 ← E

• for tetrahedral d 4 and d 9 ,

the transition is E ← T2
Orgel diagram for d1, d4, d6 (high- spin) and
d9 ions in octahedral and tetrahedral fields
 Electronic Spectroscopy in
Transition Metal Complexes
Orgel Diagrams
In an analogous manner to grouping d1, d4, d6 and d9 ions, we can consider
together d2, d3, d7 and d8 ions in octahedral and tetrahedral fields.

Two points are particularly

important:

• selection rules restrict

electronic transitions to those
between terms with the same
multiplicity


• the ground state will be a term

with the highest spin
multiplicity (Hund’s rules)

For a d2 ion the transitions will be:

3T2g (F) ← 3T1g (F)

3T1g (P) ← 3T1g (F)

3A2g (F) ← 3T1g (F)

Orgel diagram for d2, d3, d7 and d8 ions
 Electronic Spectroscopy in
Transition Metal Complexes
Exercise
The electronic spectrum of an aqueous solution of [Ni(en)3]2+ exhibits broad
absorptions with λ ︎ max ≈ 325, 550 and 900 nm. (a) Suggest assignments for the
electronic transitions. (b) Which bands are in the visible region?

Orgel diagram for d2, d3, d7 and d8 ions

 Electronic Spectroscopy in
Transition Metal Complexes
Exercise
The electronic spectrum of an aqueous solution of [Ni(en)3]2+ exhibits broad
absorptions with λ ︎ max ≈ 325, 550 and 900 nm. (a) Suggest assignments for the
electronic transitions. (b) Which bands are in the visible region?

From the Orgel diagram in the figure

the three transitions can be assigned
as follow:

900 nm assigned to 3T2g (F) ← 3A2g (F)

550 nm assigned to 3T1g (F) ← 3A2g (F)
325 nm assigned to 3T1g (P) ← 3A2g (F)

QUESTION
Why are the three transitions for
[Ni(en)3]2+ (a) spin-allowed, and
(b) Laporte-forbidden?
Orgel diagram for d2, d3, d7 and d8 ions
 Electronic Spectroscopy in
Transition Metal Complexes
Interpretation of electronic spectra: use of Racah parameters
For a d1 and d6 configurations, the energy of the absorption band in an
electronic spectrum gives a direct measure of Δ ︎ oc. The electronic spectrum of
an octahedral d2, d3, d7 or d8 ion to consist of three absorptions arising from d–d
transitions. How do we determine a value of ︎oct from such a spectrum?

Δoc
 Electronic Spectroscopy in
Transition Metal Complexes
Racah parameters
For a given electron configuration, the energies of the terms are given by
equations involving Racah parameters (A, B and C) which allow for
electron–electron repulsions.
A corresponds to an average of the total interelectron repulsion, and B and
C relate to the repulsion energies between individual d electrons.

Each term arising from a given

configuration has an energy that
may be expressed as a linear
combination of all three Racah
parameters.

For a d2 configuration a detailed

analysis shows that:

Energy of 1S = A + 14B + 7C
Energy of 1D = A – 3B + 2C
Energy of 1G = A + 4B + 2C
Energy of 3P = A + 7B
d1 ion d2 ion Energy of 3F = A – 8B
 Electronic Spectroscopy in
Transition Metal Complexes
Racah parameters - d2 configuration
Energy of 1S = A + 14B + 7C
Energy of 1D = A – 3B + 2C If C > 5B: 3F > 3P > 1D > 1G > 1S
Energy of 1G = A + 4B + 2C
Energy of 3P = A + 7B If C < 5B: 3F > 1D > 3P > 1G > 1S (Ti2+)
Energy of 3F = A – 8B

C ≈ 4B

Racah parameters for some d-block ions

 Electronic Spectroscopy in
Transition Metal Complexes
Racah parameters - d2 configuration

From the equations, the energy difference between the terms of

maximum spin multiplicity, 3P and 3F, requires the use only of the Racah
parameter B. This is true for P and F terms of a common multiplicity
arising from other dn configurations

Energy of 1S = A + 14B + 7C
Energy of 1D = A – 3B + 2C
Energy of 1G = A + 4B + 2C
Energy of 3P = A + 7B
Energy of 3F = A – 8B
 Electronic Spectroscopy in
Transition Metal Complexes
Tanabe-Sugano Diagrams
TanabeSugano diagrams are correlation diagrams that depict the energies of
electronic states of complexes as a function of the strength of the ligand field

d2 with C = 4.428B d3 with C = 4.502B

Yukito Tanabe, Satoru Sugano; J. Phys. Soc. Japan, 1954, 9, 753

 Electronic Spectroscopy in
Transition Metal Complexes
Tanabe-Sugano Diagrams
TanabeSugano diagrams are correlation diagrams that depict the energies of
electronic states of complexes as a function of the strength of the ligand field
d4 with C = 4.611B d5 with C = 4.477B

Yukito Tanabe, Satoru Sugano; J. Phys. Soc. Japan, 1954, 9, 753

 Electronic Spectroscopy in
Transition Metal Complexes
Tanabe-Sugano Diagrams
TanabeSugano diagrams are correlation diagrams that depict the energies of
electronic states of complexes as a function of the strength of the ligand field
d6 with C = 4.808B d7 with C = 4.633B

Yukito Tanabe, Satoru Sugano; J. Phys. Soc. Japan, 1954, 9, 753

 Electronic Spectroscopy in
Transition Metal Complexes
Tanabe-Sugano Diagrams
Tanabe-Sugano diagrams are correlation diagrams that depict the energies of
electronic states of complexes as a function of the strength of the ligand field
d8 with C = 4.709B

Yukito Tanabe, Satoru Sugano; J. Phys. Soc. Japan, 1954, 9, 753

 Electronic Spectroscopy in
Transition Metal Complexes
Worked example

How to identify and assign the electronic transitions observed for

[Ni(en)3]2+ in the electronic spectrum which exhibits broad
absorptions with ︎λmax ︎of 325, 550 and 900 nm

Electronic spectrum of a d8
octahedral complex

10 000 20 000 30 000

cm-1
 Electronic Spectroscopy in
Transition Metal Complexes
Worked example

How to identify and assign the electronic transitions observed for

[Ni(en)3]2+ in the electronic spectrum which exhibits broad
absorptions with ︎λmax ︎of 325, 550 and 900 nm

Electronic spectrum of a d8
octahedral complex

10 000 20 000 30 000

cm-1
 Electronic Spectroscopy in
Transition Metal Complexes
Tanabe-Sugano Diagram for d8
octahedral complexes
1A 1T
3T
g 2g 1E
g
1g Electronic spectrum of a d8
octahedral complex
1T
1g
1T
2g

3T
1g

ε
3T
2g
10 000 20 000 30 000
1A cm-1
1g

Spin allowed transitions

1E Low energy band: 3T2g (F)← 3A2g(F)
g

Intermediate energy band: 3T1g (F)← 3A2g(F)

High energy band: 3T1g (P)← 3A2g(F)

3A
2g

325, 550 and 900 nm

 Electronic Spectroscopy in
Transition Metal Complexes
Exercise
Aqueous solutions of [V(OH2)6]3+ show absorptions at 17200 and 25600
cm︎-1 assigned to the 3T2g ← 3T1g (F) and 3T1g (P) ← 3T1g (F) transitions.
Estimate values of B and ︎Δoct for [V(OH2)6]3+.

Tanabe-Sugano Diagram for the

d2 configuration
 Electronic Spectroscopy in
Transition Metal Complexes
Exercise
Aqueous solutions of [V(OH2)6]3+ show absorptions at 17200 and 25600
cm︎-1 assigned to the 3T2g ← 3T1g (F) and 3T1g (P) ← 3T1g (F) transitions.
Estimate values of B and ︎Δoct for [V(OH2)6]3+.

Let the transition energies be E2 = 25600 cm︎-1

and E1 = 17200 cm︎-1
 Electronic Spectroscopy in
Transition Metal Complexes
Exercise
Aqueous solutions of [V(OH2)6]3+ show absorptions at 17200 and 25600
cm︎-1 assigned to the 3T2g ← 3T1g (F) and 3T1g (P) ← 3T1g (F) transitions.
Estimate values of B and ︎Δoct for [V(OH2)6]3+.
 Electronic Spectroscopy in
Transition Metal Complexes
Exercise
Aqueous solutions of [V(OH2)6]3+ show absorptions at 17200 and 25600
cm︎-1 assigned to the 3T2g ← 3T1g (F) and 3T1g (P) ← 3T1g (F) transitions.
Estimate values of B and ︎Δoct for [V(OH2)6]3+.
 Electronic Spectroscopy in
Transition Metal Complexes
Interpretation of spectra of d5 metals (high spin) – Spin-forbidden
transitions

There are no spin allowed transitions for d5

high spin configurations. Extinction
coefficients are very low, though the selection
rule is relaxed by spin-orbit coupling

Ground state: 6A1g

 Electronic Spectroscopy in
Transition Metal Complexes
Effect of spin-orbit coupling
The electron has an intrinsic magnetic moment
“like a tiny magnetic bar”. These spins orientate
themselves in a magnetic field.

Similarly, there is an orbital-derived magnetic

moment for all but S terms.

The spin-orbit coupling causes splitting of some

of the degeneracies implicit in the orbital energy
level diagram.

Spin-orbit coupling is of
great importance for all
ions of the 2nd and 3th
transition series
 Electronic Spectroscopy in
Transition Metal Complexes
Atomic spin-orbit coupling parameters (cm-1)

Metal Charge on metal atom

0 1+ 2+ 3+ 4+ 5+ 6+
Ti (123) 104 131 158 * (3716) (3973)
V (179) 154 187 220 253 * (4900)
Cr (248) 219 256 296 337 378 *
Mn (334) 294 343 338 436 486 536
Fe (431) 388 441 499 554 612 673
Co (550) 500 561 625 695 760 830
Ni (691) 634 703 775 851 934 1012
Cu (857) * 870 931 1037 1127 1224
Ru (1042) 968 1082 1201 1319 1441 1564
Rh (1259) 1177 1299 1426 1567 1689 1825
Os (3381) 3174 3531 3898 4259
Ir (3909) 3690 4056 4430 4814
 Electronic Spectroscopy in
Transition Metal Complexes
The nephelauxetic effect
Electronelectron repulsions are lower in complexes than in free ions because of
electron delocalization; the nephelauxetic parameter is a measure of the extent
of d-electron delocalization on to the ligands of a complex;

This indicates that interelectronic repulsion is less in complexes and that the
effective size of the metal orbitals has increased; this is the nephelauxetic effect.

The reduction of B from its free ion value is normally reported in terms of the
nephelauxetic parameter, β:
The softer the ligand,
B(complex) the smaller the
β= nephelauxetic parameter
B( free ion)
 Electronic Spectroscopy in
Transition Metal Complexes
The nephelauxetic effect
The reduction of B from its free ion value is normally reported in terms of the
B(complex)
nephelauxetic parameter, β =
B( free ion)

For octahedral [FeF6]3-:

Therefore, the reduction in

The nephelauxetic effect can be parameterized interelectronic repulsion in
and the values shown in the table used to going from the gaseous Fe3+
estimate the reduction in electron–electron ion to [FeF6]︎3-︎ is ≈19%
repulsion upon complex formation
 Magnetic Properties in
Transition Metal Complexes
Cooperative magnetism
In solids, the spins on neighbouring metal centres may interact to produce
magnetic behavior, such as ferromagnetism and anitferromagnetism, that are
representative of the whole solid

The magnetic susceptibility, χ, of a material is a measure of how easy it is to

align electron spins with the applied magnetic field in the sense that the
induced magnetic moment is proportional to the applied field, with the
constant of proportionality.
 Magnetic Properties in
Transition Metal Complexes
A paramagnetic, tetrahedral Pd(II) complex
Paramagnetism arises from unpaired electrons
 Magnetic Properties in
Transition Metal Complexes
A paramagnetic, tetrahedral Pd(II) complex

Crystal field splitting diagrams for some common fields referred to

a common barycentre; splittings are given with respect to ︎Δoct
 Magnetic Properties in
Transition Metal Complexes
Cooperative magnetism
Compounds are classified as diamagnetic if they are repelled by a magnetic
field and paramagnetic if they are attracted by a magnetic field.

The magnitude of the paramagnetism of a complex is commonly reported in

terms of the magnetic dipole moment (μ) it possesses
n
S=
2
n is the number of
unpaired electrons

The effective magnetic moment, ︎μeff, can be obtained from the

experimentally measured molar magnetic susceptibility (in Bohr Magnetons)

Where 1μB = eh /4πme; k = Boltzmann constant;

L = Avogadro number; μ0 = vacuum permeability;
T = temperature in kelvin
 Magnetic Properties in
Transition Metal Complexes
Calculation of magnetic susceptibility
The Gouy method makes use of the interaction between unpaired electrons
and a magnetic field, and therefore, it is use to calculate χm

Gaussian units

The change in weight caused by the

movement of the sample into the field is
recorded, and from the associated force it
is possible to calculate the magnetic
Schematic representation of a Gouy balance susceptibility of the compound
 Magnetic Properties in
Transition Metal Complexes
Calculation of magnetic susceptibility
For metal complexes in which the spin quantum number S is the same as for
the isolated gaseous metal ion, the spin-only formula can be applied to find
the number of unpaired electrons

Spin-only values of μ
︎ eff compared with approximate ranges of observed magnetic
moments for high-spin complexes of first row d-block ions
 Magnetic Properties in
Transition Metal Complexes
Exercise: Magnetic moments: spin-only formula

At room temperature, the observed value of ︎μeff for [Cr(en)3]Br2 is 4.75 μB. Is
the complex high- or low-spin?

Low-spin will have two unpaired electrons (n = 2), and high-spin will have
four (n = 4)
 Magnetic Properties in
Transition Metal Complexes
Exercise: Magnetic moments: spin-only formula

Given that (at 293K) the observed value of μ

︎ eff for [VCl4(MeCN)2] ︎ is 1.77 ︎μB,
deduce the number of unpaired electrons and confirm that this is consistent
with the oxidation state of the V atom
 Magnetic Properties in
Transition Metal Complexes
Spin and orbital contributions to the magnetic moment
The energy difference between
adjacent states with J values of
J′ and (J′ + 1) is given by the
expression (J′ + 1)λ where λ is
3F4
called the spin–orbit coupling
constant 4λ
3F3

These very small energy 3F2

3λ
differences are analyzed in EPR
spectroscopy

In a magnetic field, each state with

a different J value splits again to
2J + 1
give (2J + 1) different levels
separated by gJ μB B0 where gJ is a
constant called the Landé splitting
factor and B0 is the magnetic field
Splitting of the terms of a d2 ion (not to scale)
 Magnetic Properties in
Transition Metal Complexes
Spin and orbital contributions to the magnetic moment

The value of λ varies from a fraction of a cm︎-1 for the very lightest atoms to
a few thousand cm︎-1 for the heaviest ones

if the separation of energy levels is large, the magnetic moment is given by

the following equation:

This equation works very well for the calculation of the magnetic moment of
lanthanoid ions (λ = 1000 cm-1), however, for d-block metal ions, it gives results that
correlate poorly with experimental data
 Magnetic Properties in
Transition Metal Complexes
Spin and orbital contributions to the magnetic moment

For many (but not all) first row metal ions, λ is very small and the spin
and orbital angular momenta of the electrons operate independently

If there is no contribution The van Vleck

from orbital motion: formula:
d5 configuration → Mn2+
or Fe3+ (L = 0) The spin-only
formula:

Calculated magnetic moments for first row d-block metal ions in high-spin
complexes at ambient temperatures
 Magnetic Properties in
Transition Metal Complexes
The effects of temperature on ︎μeff
When spin–orbit coupling is large, ︎μeff is highly dependent on T. For a
given electronic configuration, the influence of temperature on μeff can
be seen from a Kotani plot of ︎μeff against kT/λ

For Mn3+ and Cr2+ μeff (298 K)

lies on the near-horizontal part
of the curve, changing the
temperature has little effect
on μeff

For heavier metal ions, μ

︎ eff
is sensitive to changes in
temperature, specially for
Os4+ (third raw)
 Magnetic Properties in
Transition Metal Complexes
Spin crossover complexes
With some complexes, normally of the 3d-series metals, there is only a
very small energy difference between the two states, leading to the
possibility of spin crossover complexes

This may be initiated by a change in pressure

(e.g. a low- to high-spin crossover for [Fe(CN)5
(NH3)]3- at high pressure) or temperature (e.g.
octahedral [Fe(phen) 2 (NCS-N) 2 ]︎ , octahedral
[FeTp 2 ] 2+ and the square-based pyramidal
complex below undergo low- to high-spin
crossovers at 175, 391 and 180 K, respectively

Tp = tris-pyrazolil borate
 Magnetic Properties in
Transition Metal Complexes
Spin crossover complexes
The change in the value of ︎μeff which accompanies the spin crossover may be
gradual or abrupt

A preference normally
exists for the low-spin
state under high pressure
and low temperature

The change to high-spin might be (a) A hysteresis loop that can occur
abrupt, (b) gradual, or (c) stepped with some spin crossover systems
 Magnetic Properties in
Transition Metal Complexes
Spin crossover complexes - Mössbauer spectroscopy
Mössbauer spectroscopy can be used to study spin-crossover transitions

The structure (X-ray diffraction) of Mössbauer spectra of crystallized

the [Fe{HC(3,5-Me2pz)3}2]2+ cation [Fe{HC(3,5-Me2pz)3}2]I2
 Magnetic Properties in
Transition Metal Complexes
Fe r r o m a g n e t i s m , a n t i f e r r o m a g n e t i s m a n d
ferrimagnetism
For a paramagnetic material, the magnetic susceptibility, ︎, is inversely
proportional to temperature. This is expressed by the Curie law:
C
χ = , where C = Curie constant and T = temperature in K
T
Paramagnetism Ferromagnetism

Antiferromagnetism Ferrimagnetism

In a ferromagnetic material, large domains of magnetic dipoles are aligned in the

same direction; in an antiferromagnetic material, neighboring magnetic dipoles are
aligned in opposite directions

When the paramagnetic species are very close together or are separated by a species
that can transmit magnetic interactions (as in many d-block metal oxides, fluorides
and chlorides), the metal centres may interact (couple) with one another
 Magnetic Properties in
Transition Metal Complexes
Fe r r o m a g n e t i s m , a n t i f e r r o m a g n e t i s m a n d
ferrimagnetism
Ferromagnetism leads to greatly enhanced paramagnetism as in iron metal
at temperatures of up to 1043 K (the Curie temperature, TC ). Above the
Curie temperature, a ferromagnetic material obeys the Curie–Weiss law

Paramagnetic

On cooling a sample,
ferromagnetic ordering occurs
at the Curie temperature, TC
 Magnetic Properties in
Transition Metal Complexes
Fe r r o m a g n e t i s m , a n t i f e r r o m a g n e t i s m a n d
ferrimagnetism
Antiferromagnetism occurs below the Néel temperature, TN ; as the
temperature decreases, less thermal energy is available and the
paramagnetic susceptibility falls rapidly

The classic example of antiferromagnetism is MnO, which has a

NaCl-type structure and a Néel temperature of 118 K