TANABE SUGANO

DIAGRAM FOR
TRANSITION
Presented by METAL
R.Sridhar
COMPLEXES
II Msc Chemistry
DEFINITION

• The Tanabe-Sugano diagram is a plot of orbital

energy as a function of the Racah parameter B
vs Δo/B.
• Yukito Tanabe and satoru sugano- On the
Absorption spectra of "complex ions"-1954.
• Explain the absorption spectra of octahedral
complex ions.
• used in coordination chemistry to predict
absorptions in the UV, visible and IR
electromagnetic spectrum of coordination
compounds.
• can be used for both high spin and low spin
complexes.
• Ground state is taken as constant reference
and energies of all other terms are plotted
with respect to ground state.
TS diagram for d2-d8 systems
TS diagram for d2-d8 systems
TS diagram for d2-d8 systems

Why TS diagram does not require for d1,d9 & d10 systems?

• In d1 & d9 systems, only one single electron does

undergoes transition from T2g to Eg and vice versa. So
there is no electron repulsion and it takes minimum
amount of energy.
• In d10 system, there are no d-d electron transitions in
d10 metal complexes because the d orbitals are
completely filled. Thus, UV-vis absorption bands are not
observed and a Tanabe–Sugano diagram does not exist.
How do you use?
For example, we take
3
T1g -> 3A2g is also available for V3+ complex. But
[V(H2O)]3+ UV spectrum…… that is not in UV region.

3
T1g -> 3T1g

3
T1g -> 3T2g Here, V1 = 17794 cm-1
V2 = 25707 cm-1
How do you use?
Step 1 : Find energy ratio

V2/V1 = 25707/17794 = 1.44

Step 2 : Find o/B by using Sugano diagram

V2/V1 = 1.44

31
How do you use?
Step 1 : Find energy ratio

V2/V1 = 25707/17794 = 1.44

Step 2 : Find o/B by using Sugano diagram

So o/B = 31

V2/V1 = 1.44

31
How do you use?

Step 3 : Determine the Racah parameter(B) using

TS diagram

So we know o/B = 31

31
For V2, E/B = 41

V1, E/B = 29

31
How do you use?

Step 3 : Determine the Racah parameter(B) using

TS diagram

For V2, E/B = 41 V2/B = 41

25707/B = 41

B = 627cm-1

For V1, E/B = 29 V1/B = 29

17794/B = 29

B = 613cm-1
31

Bavg = 620 cm-1

How do you use?

Step 4 : Determine o

Bavg = 620 cm-1

2.38eV
o /B = 31

o/620 = 31

o = 19229 cm-1

So o = 19229 cm-1 or 2.38eV or 520nm

10Dq = o

10Dq = 2.38

Dq = 0.238 eV
How do you use?
For example, we take So o = 520nm
[V(H2O)]3+ UV spectrum……

3
T1g -> 3T1g

3
T1g -> 3T2g H2O ligand is weak field ligand
and have hign spin. So the
absorption range is increased
from 520nm to 562nm.
Nephelauxetic ratio
For example, [V(H2O)]3+ complex Racah parameter values
are B1 = 613cm-1 and B2 = 627cm-1 …
So the Nephalauxetic ratio is …

B1/B2 = 613/627 = 0.978

Hence, inner electronic repulsion has been decreased during the process of complexation.

2.38eV

So the weak field ligand require energy to split the d orbital for electron transfer from the
ligand to metal.
Advantages

• Tanabe-Sugano diagrams can be used for both high spin and low spin
complexes, unlike Orgel diagrams which apply only to high spin
complexes.
• In a Tanabe-Sugano diagram, the ground state is used as a constant
reference, in contrast to Orgel diagrams.
• However, if the ligand field splitting energy, 10Dq, is greater than the
electron-repulsion energy, then Orgel diagrams fail in determining
electron placement whereas Tanabe-Sugano diagrams can be applied
to situations when 10Dq is significantly greater than electron
repulsion.
Applications

• Shows the energy splitting of the spectral terms with the increase of
the ligand field strength.
• It is even easier to predict the possible transitions and their relative
intensity.
• Used to predict the position of electronic transition.
• Tanabe-Sugano diagrams are very useful tools for analyzing UV-vis
spectra:
 they are used to assign bands.
 calculate Dq values for ligand field splitting.
THANK YOU