The formation of coloured compounds

❑ Why do we observe colour? (what is seen actually isn’t there)

When light falls on any substance, some of it is absorbed and the rest is reflected. The
reflected light reaches our eye, which is the color that we see. For example, if a compound
absorbs the red, it appears green (i.e., transmitted light), i.e., the colour is the complementary
colour.

❑ Transition metal ions generally possess one or more unpaired electrons. When visible light
falls on a transition metal compound or ion, an electron from a lower energy d orbital is
excited to a higher energy d orbital, and the energy of excitation corresponds to the
frequency of light absorbed.

Most of the transition metal compounds are coloured. It arises due to the following reasons:
(i) d – d transition
(ii) Charge transfer (LMCT, MLCT)

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purple light is absorbed, the complex
appears yellow

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 Colors of the transition metal complexes

• As electron transition takes place from one group of d orbitals to the other, it is called d – d transition.
•
• Metal ions which have d0, d5 and d10 configurations are colourless

• The color of the TM complex is dependent on how big the energy difference between the two d levels

• The colour of the transition metal complex is dependent on the nature of the ligand.

[Ni(H2O)6]2+ is green and [Ni(NH3)6]2+ is

blue. Why?

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[Cr(H2O)6]3+
 Questions

• There are two solutions, one orange and one blue. Both solutions are known to be made up of a
cobalt complex; however, one has chloride ions as ligands, while the other has ammonia ligands.
Which solution is expected to be orange?

NH3 is a stronger ligand than Cl-, which means that the complex involving NH3 has a greater ∆, and
complex will be low spin. Because of the larger ∆, the electrons absorb higher energy photons, and the
solution will have the appearance of a lower energy color. Since orange light is less energetic than blue
light, the NH3-containing solution is predicted to be orange

• Would you expect a violet solution to be high spin or low spin? What about a red solution?

It would be high spin. The complementary color of violet is yellow, which has a wavelength of 570
nm. For a red solution, the complementary color absorbed is green, with a wavelength of 530 nm,
so it would be considered low spin.
The molar absorption coefficient, molar extinction coefficient,or molar absorptivity(ε), is a measurement of how strongly a
chemical species absorbs light at a given wavelength. Intensity of Color
The maximum value of ε in a band, εmax, is a convenient guide to the absorption intensity.

The intensity of a transition is governed by selection rules. 12

Absorption and Emission Spectra
• When electromagnetic radiations are passed through the compound, they may be absorbed to induce electronic,
vibrational and rotational transitions in the molecules. Only the radiation supplying the required quantum (photon)
of energy is absorbed and the remaining portion of the incident radiation is transmitted.

• The wavelengths or frequencies of the absorbed radiations are measured with the help of a spectrometer.

• Generally, a spectrometer records an absorption spectrum as a plot of the intensity of absorbed or transmitted
radiations versus their wavelengths or frequencies. Such spectra which are obtained by absorption of
electromagnetic radiations are called absorption spectra.

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 Dissolving CoCl2in water produces a pale pink solution of [Co(H2O)6]2+, but on adding HCl
tetrahedral [CoCl4]2‐ forms, which has a very intense blue color. How do you explain this color
changes?

The intensity of the color can be explained by selection rules

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 Laporte Selection Rule
Statement :This rule states that transitions between the orbitals of the same sub shell are forbidden. OR During an
electronic transition the azimuthal quantum number can change only by ±1 (Δl= ±1)

In a molecule or ion possessing a centre of symmetry,

transitions are not allowed between orbitals of the
same parity

The forbidden transitions are s → s, d → d

The geometries affected by this rule include octahedral

and square-planar complexes. The rule is not applicable
to tetrahedral complexes as it does not contain a center of
symmetry.

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 Spin Selection Rule
Statement: This rule states that transitions that involve a change in spin multiplicity are forbidden.
According to this rule, any transition for which ΔS= 0 is allowed and ΔS≠0 is forbidden

During an electronic transition, the electron should not change its spin

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 Relaxation of the selection rules
There are three mechanisms that allow ‘forbidden’ electronic transitions to become somewhat ‘allowed’ resulting
in some intensity of the color expected
• 1. Vibronic Coupling: The Laporte selection rule can be circumvented, either due to various ligands around the molecule
disrupting the perfect symmetry around the complex, or because the molecule can vibrate to remove the centre of symmetry.

• The interaction between electronic and vibrational modes is called vibronic coupling and means that d-d transitions are
observed. However, they are often not very intense due to energy expended in vibration.

• The intensity of vibronic bands increases with temperature as vibrational amplitudes increase.

• Larger transition metals (2nd/3rd row) cause a large splitting factor (Δ) which makes the vibronic coupling more efficient.

• During some unsymmetrical vibrations of a molecule there can be

a temporary/transient loss of the centre of symmetry. Loss of
center of symmetry helps to overcome the Laporte selection rule.
• Also time required for an electronic transition to occur (life time
10‐18 sec) is much less than the time required for a vibration to
occur (life time 10-13 sec)

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 Relaxation of the selection rules
2. Mixing of states:
• The states in a complex are never pure, and so some of the symmetry properties ( g or u) of neighboring states
become mixed into those of the states involved in a ‘forbidden’ transition. For example mixing of d (gerade) and p
(ungerade) orbitals results in partial breakdown of the Laporte rule

• Complexes with tetrahedral symmetry do not have a center of inversion, which allows easier mixing of levels
to give more intense transitions.

• This is further magnified by the fact that the t2 orbitals in Td complexes have the same symmetry as the (n+1)p
orbitals, so e to t2 has a partly d-p character. This means that the Angular Momentum Selection Rule is also
partly satisfied, making the intensity even stronger.

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Laporte selection rule

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Summary

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 Q1. 1 mmol of VCl2, CrCl2 and MnCl2 were separately dissolved in 10 mL of H2O. Which of these
solutions will produce the most intense colour and why?

Q2. Why the colour of trans [Co(en)2F2] + is less intense than that of cis [Co(en)2F2]+ ?

Q3. The correct order of intensity of the d-d transitions in the complexes of a 3d-transition metal ion

Q4. The intensity of absorption bands in [CoCl4]2- is almost a hundred times greater than in [MnCl4]2-

Q5. In the following pairs of complexes which one will show higher absorption intensity in the UV-vis
spectra? Justify your answer.
(a) [Fe(H2O)6]3+, [Fe(H2O)6]2+
(b) [FeCl4]2–, [Co(NH3)6]3+
(c) cis-[Cu(en)2Cl2]2+, trans-[Cu(en)2Cl2]2+ (en = ethylenediamine)
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 Charge Transfer Spectra

Potassium chromate Potassium dichromate Potassium permanganate.

[Fe(phen)3]2+ (blood red)

Prussian Blue

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 Ligand to Metal Charge Transfer (LMCT)
• If the ligand molecular orbitals are full, charge transfer may occur from the ligand molecular orbitals to the
empty or partially filled metal d-orbitals. The absorptions that arise from this process are called ligand-to-metal
charge-transfer bands (LMCT)
• LMCT results in the reduction of the metal centre.

• Ligand: should be low energy filled orbital, pi donor ligands (example??)

• Metal: vacant orbital, should be in higher oxidation state
What will happen to LMCT energy 1) when moving down the group? 2) left to right?

Why KMnO4 is intense color?

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 Metal to Ligand Charge Transfer Bands (MLCT)
• If the metal is in a low oxidation state (electron-rich) and the ligand possesses low-lying empty orbitals (e.g.,
CO) then a metal-to-ligand charge transfer (MLCT) transition may occur. MLCT results in the oxidation of the
metal centre.

• MLCT transitions are common for coordination compounds having π-acceptor ligands. Upon the absorption
of light, electrons in the metal orbitals are excited to the ligand π* orbitals.

• Ligand: should have vacant orbital, pi acceptor ligands (example??)

• Metal: Filled orbital, should be in low oxidation state (electron-rich)

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Journal of Industrial and Engineering Chemistry, 2018, 61, 381-387.
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