Universidad del Valle

Inorganic Chemistry II

Prof. Renso Visbal Acevedo Departamento Química

email: renso.visbal@correounivalle.edu.co
 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(III)

[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 d4 and d9, the

transition is T2g ← Eg

• for tetrahedral d1 and d6, the

transition is T2 ← E

• for tetrahedral d4 and d9 , 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 ︎Δoct 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
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

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
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
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
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
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
cm-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
cm-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
cm-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
cm-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
Luminescence
A complex is luminescent if it emits radiation after it has been electronically
excited by the absorption of radiation.

Fluorescence is radiative decay from an

excited state of the same multiplicity as
the ground state. The transition is spin-
allowed and is fast; fluorescence half-lives
are a matter of nanoseconds.
SOC
Phosphorescence is radiative decay from a
state of different multiplicity from the
ground state. It is a spin-forbidden process,
and hence is often slow

The transitions responsible for the

absorption and luminescence of Cr3+
ions in ruby
 Electronic Spectroscopy in
Transition Metal Complexes
Luminescence
A complex is luminescent if it emits radiation after it has been electronically
excited by the absorption of radiation.

SOC

The absorption and The transitions responsible for the

phosphorescence spectra of absorption and luminescence of Cr3+
[Ru(bpy)3]2+ ions in ruby
 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

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
nis 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

SI 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 g J μB B0 where g J 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 cm-1 for the very lightest atoms to
a few thousand cm-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:

The van Vleck The spin-only

formula 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 (λ = spin-orbit coupling constant)

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, μeff

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, abrupt or even stepped

A preference normally exists for

the low-spin state under high
pressure and low temperature

The change to high-spin might be (a)

abrupt, (b) gradual, or (c) stepped
 Magnetic Properties in
Transition Metal Complexes
Spin crossover complexes - Mössbauer spectroscopy
Mössbauer spectroscopy can be used to study spin-crossover transitions

High spin

change to a
low-spin state

transition is
Low spin
complete

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, χ , 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