Tanabe-Sugano Diagrams

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ChemWiki: The Dynamic Chemistry E-textbook > Inorganic Chemistry > Crystal Field Theory > Tanabe-Sugano Diagrams
Tanabe-Sugano Diagrams
Contributor: Evan Sarina, UC Davis
Tanabe-Sugano diagrams are used in coordination chemistry to predict

electromagnetic absorptions of metal coordination compounds.
INTRODUCTION
Tanabe-Sugano diagrams are used in coordination chemistry to predict
electromagnetic absorptions of metal coordination compounds of tetrahedral and
octahedral complexes. The analysis derived from the diagrams can also be
compared to experimental spectroscopic data. Armed with spectroscopic data, an
approximation to the crystal field splitting energy (10Dq), generated by ligands
attached to a metal center, can be found.
CRYSTAL FIELD SPLITTING ENERGY
Within Crystal Field Theory, the interaction of the metal and ligand arise from
the positive charge of the metal and negative charge on the ligands. The theory is
developed by looking at the five degenerate d-orbitals and how the energies are
changed on being surrounded by the negative point charges of the ligands. As the
ligands are moved closer to the metal the repulsion between the electrons of the
metal and ligands break the degeneracy of the d-orbitals. In the case of an
octahedral complex 6 ligands surround a metal center with a single pair on each
axis. This raises the energies of d x^2-y^2, dz^2relative to those of dxy dxz dyz. This
energy split is called oct. The tetrahedral energy split is about 4/9oct.1
RACAH PARAMETERS
Racah parameters were generated as a means to describe the effects of
electron-electron repulsion within the metal complexes. The Racah parameters
are A, B and C.
In
the
case
of
Tanabe-Sugano
diagrams
each
electron
configuration split has an energy that can be related by the B value. A is ignored
because it is roughly the same for any metal center and C generally approximated
as being 1/4B. What Brepresents is an approximation of the bond strength
between
the
ligand
and
metal.1 Comparisons
between
tabulated
free
ion B and B of a coordination complex is called the nephelauxetic ratio (the effect
of reducing electron-electron repulsion via ligands). This effect is what gives rise
to the spectrochemical series of ligands described later.
=complexfreeion
PARAMETERS2
The x-axis in a Tanabe-Sugano diagram is in terms of the crystal field
splitting parameter, 10Dq, or oct, scaled by the B Racah Parameter. The y-axis is
in terms of energy of a electronic transition, E, scaled by B. Each line represents
the energy of an electronic state while varying the strength of octahedral ligand
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field. And while only a few electronic states are spin allowed the spin forbidden
electron transitions are included since spin forbidden transitions can appear in
spectrum. Each term symbol is created from the splitting of term symbols from
spherical to octahedral symmetry. With the relative energy ordering of the states
are determined via Hund's rules.
Diagrams for d4, d5, d6, and d7 metal ions have a discontinuity in energies as
the ligand field is varied. The discontinuity, shown with the vertical line,
represents complexes changing from high-spin to low-spin complexes. At the line,
the spin pairing energy is equal to the crystal field splitting energy. To the left of
the line metal complexes are high-spin as the spin pairing energy is greater than
that of the ligand field splitting. To the right of the line metal complexes are lowspin as the spin pairing energy is less than that of the ligand field splitting energy.
DIAGRAMS3-4
d2 Tanabe-Sugano
d3 Tanabe-Sugano
d4 Tanabe-Sugano
d5 Tanabe-Sugano
diagram
diagram
diagram
diagram
Note: Each of the images

is a thumbnail clicking on
one will expand the
image.
d6 Tanabe-Sugano
d7 Tanabe-Sugano
d8 Tanabe-Sugano
diagram
diagram
diagram
HOW TO USE THE DIAGRAMS

1. Before looking at the diagrams the d-configuration of the metal ion must be
determined.
2. Choose the
configuration
appropriate
Tanabe-Sugano
diagram
matching
the
(http://chemistry.bd.psu.edu/jircitano/TSdiagram.pdf has
dfull
page diagrams necessary for measurements).

3. Take a spectrum of the complex and identify max for spin-allowed (strong
4.
intensity) and spin forbidden (weak intensity) transitions.

Convert max to wavenumbers and generate energy ratios relative to the
lowest allowed transition. (i.e. E2/E1and E3/E1)
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5.
Using a ruler, slide it across the printed diagram until the E/B ratios between
lines is equivalent to the ratios found in step 4.

6. Solve for B using the E/B values (y-axis, step 4) and oct/B (x-axis, step 5) to
yield the ligand field splitting energy 10Dq.
EXAMPLE 1
A Cr3+ metal complex has strong transitions and maxat 431.03, 781.25 and 1250
nm determine the oct for this complex.
SOLUTION
1.
Cr has 6 electrons. Cr3+ has three electrons so a d-configuration of d3
2.
Locate the d3 Tanabe-Sugano diagram
3.
Convert to wavenumbers:
107(nm/cm)/(1250 nm)= 8000 cm-1
107(nm/cm)/(781.25 nm)= 13600 cm-1
107(nm/cm)/(431.03 nm)= 23200 cm-1
4.
Allowed transitions are 4T1g<-4A2g,4T1g<-4A2g and 4T2g<-4A2g
5.
6.
Energy cm-
Ratios
Transition
lowest
T1g<-4A2g
23200
2.9
T1g<-4A2g
13600
1.7
T2g<-4A2g
8000
to
Sliding the ruler perpendicular to the x-axis yields the following values:
oct/B
10
20
30
40
Height E(3)/B
29
45
64
84
Height E(2)/B
17
30
40
51
Height E(1)/B
10
20
30
40
Ratio E(3)/E(1)
2.9
2.25
2.13
2.1
Ratio E(2)/E(1)
1.7
1.5
1.33
1.275
Based
on
the
two
tables
above
it
should
be
assessed
the oct/B value is 10. B is found by finding the dividing E by the height.
Energy cm-1
Height
23200
29
800
13600
17
800
that
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8000
7.
10
800
Next multiply oct/B by B to yield the octenergy. 10*800 = 8000 cm-1=oct

Each problem is of varying complexity as several steps may be needed to
find the correct oct/B values that yield the proper energy ratios.
NEPHELAUXETIC EFFECT
Imagine you had an abundance of V(H2O)63+ (d2) which has two absorptions. If
you had no other available metal centers, but an abundance of ligands, the
complex's absorption spectrum (therefore
its
color)
could
be changed via
application of the spectrochemical series:

I < Br < S2 < SCN < Cl < NO3 < N3 < F < OH < C2O42 H2O <
NCS < CH3CN < py (pyridine) < NH 3 < en (ethylenediamine) < bipy (2,2'bipyridine) < phen (1,10-phenanthroline) < NO2 < PPh3 < CN CO
If you wanted higher energy absorptions (shift toward purple colors) you use
ligands to the right of H 2O and if you wanted redder colors attach ligands to the
left of H2O. Here you could measure the nephelauxetic ratio of the ligands to
compare how each ligand modifies the BRacah parameter. The series of
complexes would also serve as a very good demonstration for a classroom. The
reason behind modifying metal ligands has implications for commercial products.
Unique colors in ceramics and glass products can be traced back to many metal
compounds.
REFERENCES
1. H.A.O. Hill, P. Day. Physical Methods in Advanced Inorganic Chemistry. John
Wiley & Sons, Inc. 1968.
2. Tanabe, Yukito; Sugano, Satoru (1954). "On the absorption spectra of
complex ions I". Journal of the Physical Society of Japan 9 (5): 753766.
3. Tanabe, Yukito; Sugano, Satoru (1954). "On the absorption spectra of
4.
complex ions II". Journal of the Physical Society of Japan 9 (5): 766779
Tanabe, Yukito; Sugano, Satoru (1956). "On the absorption spectra of
complex ions III". Journal of the Physical Society of Japan 11 (8): 864877.
Outside Links
http://en.wikipedia.org/wiki/Tanabe-Sugano_diagram
http://wwwchem.uwimona.edu.jm/courses/Tanabe-Sugano/TScalcs.html
http://www.luc.edu/faculty/spavko1/c340/lect/Lect-14.pdf
http://chemistry.bd.psu.edu/jircitano/TSdiagram.pdf
PROBLEMS
1. For a d7 metal ion determine the energy ratios for allowed transitions at
2.
oct/B of 20.
For a d6metal ion of oct/B = 30 and B=530 cm-1 what would the energies of
the 5 allowed transitions be? How many are in the UV-Vis range? How many
3.
are in the IR range?

Write out the allowed transitions for a d5 metal ion in a E/B> 28 ligand field.
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A d4 complex exhibits absorptions at 5500 cm-1 (strong) and 31350 cm-
4.
1
(weak). What are the transitions that are being exhibited in the complex?
What is the corresponding oct for the complex?

5. A spectrum of d7 metal complex seemingly exhibits only two intense
transitions. What is the oct/B that this situation occurs? Please use reference
to specific transitions and energy splitting.
ANSWERS
1. oct/B of 20 yields E/B values of 38, 32, 18. Ratios then are 2.11 and 1.78
2. oct/B = 30 yields E/B heights of 27, 40, 57, 65, 85. Energies are then 14310,
21200, 30210, 34450 and 45050 cm-1. All are in the UV-Vis range. *note you
need to infer the E/B value for the last transition as the diagram does not
extend that far up.
3. 2A2g<-2T2g, 2T1g<-2T2g, 2Eg<-2T2g, and 2A1g<-2T2g.
4. 31,350/5,500 gives a ratio of 5.7/1. The only oct/B value that matches is at
10. B value is then 550 cm-1. octequals 5500 cm-1.
5. Three transitions are generated at low oct/B. However, at about a value
of oct/B = 13 the transitions 4A2g<-4T1g, and 4T1g<-4T1g have the same energies
which results in the appearance of only two absorptions.

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Page 1 of 5

Tanabe-Sugano diagrams are used in coordination chemistry to predict

Note: Each of the images

HOW TO USE THE DIAGRAMS

page diagrams necessary for measurements).

intensity) and spin forbidden (weak intensity) transitions.

lines is equivalent to the ratios found in step 4.

Next multiply oct/B by B to yield the octenergy. 10*800 = 8000 cm-1=oct

application of the spectrochemical series:

are in the IR range?

What is the corresponding oct for the complex?

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