THE COLOURS OF COMPLEX METAL

IONS

This page is going to take a simple look at the origin of colour in

complex ions - in particular, why so many transition metal ions
are coloured. Be aware that this is only an introduction to what
can grow into an extremely complicated topic.

Why do we see some compounds as being coloured?

White light

You will know, of course, that if you pass white light through a
prism it splits into all the colours of the rainbow. Visible light is
simply a small part of an electromagnetic spectrum most of
which we can't see - gamma rays, X-rays, infra-red, radio waves
and so on.

Each of these has a particular wavelength, ranging from 10-16

metres for gamma rays to several hundred metres for radio
waves. Visible light has wavelengths from about 400 to 750 nm.
(1 nanometre = 10-9 metres.)

The diagram shows an approximation to the spectrum of visible

light.

Important: This isn't a real spectrum - it's a made-up

drawing. The colours are only an approximation, and so are
the wavelengths assigned to them. Anyone choosing to use
this spectrum as anything more than an illustration should be
aware that it lacks any pretence of accuracy!

Why is copper(II) sulphate solution blue?

If white light (ordinary sunlight, for example) passes through

copper(II) sulphate solution, some wavelengths in the light are
absorbed by the solution. Copper(II) ions in solution absorb light
in the red region of the spectrum.

The light which passes through the solution and out the other
side will have all the colours in it except for the red. We see this
mixture of wavelengths as pale blue (cyan).

The diagram gives an impression of what happens if you pass

white light through copper(II) sulphate solution.
Working out what colour you will see isn't easy if you try to do it
by imagining "mixing up" the remaining colours. You wouldn't
have thought that all the other colours apart from some red
would look cyan, for example.

Sometimes what you actually see is quite unexpected. Mixing

different wavelengths of light doesn't give you the same result as
mixing paints or other pigments.

You can, however, sometimes get some estimate of the colour

you would see using the idea of complementary colours.

Complementary colours

If you arrange some colours in a circle, you get a "colour wheel".

The diagram shows one possible version of this. An internet
search will throw up many different versions!

Colours directly opposite each other on the colour wheel are

said to be complementary colours. Blue and yellow are
complementary colours; red and cyan are complementary; and
so are green and magenta.

Mixing together two complementary colours of light will give you

white light.

Beware: That is NOT the same as mixing together paint

colours. If you mix yellow and blue paint you don't get white
paint. Is this confusing? YES!

What this all means is that if a particular colour is absorbed from

white light, what your eye detects by mixing up all the other
wavelengths of light is its complementary colour. Copper(II)
sulphate solution is pale blue (cyan) because it absorbs light in
the red region of the spectrum. Cyan is the complementary
colour of red.
 Note: If you are interested in understanding the relationship
between colour absorbed and colour seen (beyond the very
basic description above), find your way to lesson 2 ("Color
and Vision") of "Light Waves and Vision" on The Physics
Classroom. I'm not giving a direct link to those pages,
because that site is still developing and it is safer to give a link
to the front page of the site. This is the most understandable
explanation I have found anywhere on the web.

The origin of colour in complex ions

Transition metal v other metal complex ions

What is a transition metal?

We often casually talk about the transition metals as being those

in the middle of the Periodic Table where d orbitals are being
filled, but these should really be called d block elements rather
than transition elements (or metals).

Note: If you don't understand about the filling of orbitals in

the Periodic Table, then you must follow this link before you
go on.

Use the BACK button on your browser to return to this page.

This shortened version of the Periodic Table shows the first row
of the d block, where the 3d orbitals are being filled.

The usual definition of a transition metal is one which forms

one or more stable ions which have incompletely filled d
orbitals.

Note: The most recent IUPAC definition includes the

possibility of the element itself having incomplete d orbitals as
well. This is unlikely to be a big problem (it only really arises
with scandium), but it would pay you to learn the version your
syllabus wants. Both versions of the definition are currently in
use in various UK-based syllabuses.

If you are working towards a UK-based exam and haven't got

a copy of your syllabus, follow this link to find out how to get
one. Use the BACK button on your browser to return quickly
to this page.
Zinc with the electronic structure [Ar] 3d104s2 doesn't count as a
transition metal whichever definition you use. In the metal, it has
a full 3d level. When it forms an ion, the 4s electrons are lost -
again leaving a completely full 3d level.

At the other end of the row, scandium ( [Ar] 3d14s2 ) doesn't

really counts as a transition metal either. Although there is a
partially filled d level in the metal, when it forms its ion, it loses
all three outer electrons.

The Sc3+ ion doesn't count as a transition metal ion because its
3d level is empty.

Some sample colours

The diagrams show the approximate colours of some typical

hexaaqua metal ions, with the formula [ M(H2O)6 ] n+. The
charge on these ions is typically 2+ or 3+.

Note: If you aren't happy about naming complex ions, you

might find it useful to follow this link.

Use the BACK button on your browser to return to this page.

Non-transition metal ions

These ions are all colourless. (Sorry, I can't do genuinely

colourless!)

Transition metal ions

The corresponding transition metal ions are coloured. Some, like

the hexaaquamanganese(II) ion (not shown) and the
hexaaquairon(II) ion, are quite faintly coloured - but they are
coloured.

So . . . what causes transition metal ions to absorb wavelengths

from visible light (causing colour) whereas non-transition metal
ions don't? And why does the colour vary so much from ion to
ion?

The origin of colour in complex ions containing transition

metals

Complex ions containing transition metals are usually coloured,

whereas the similar ions from non-transition metals aren't. That
suggests that the partly filled d orbitals must be involved in
generating the colour in some way. Remember that transition
metals are defined as having partly filled d orbitals.

Octahedral complexes

For simplicity we are going to look at the octahedral complexes

which have six simple ligands arranged around the central metal
ion. The argument isn't really any different if you have
multidentate ligands - it's just slightly more difficult to imagine!

Note: If you aren't sure about the shapes of complex ions,

you might find it useful to follow this link before you go on.
You only need to read the beginning of that page.

If you don't know what a ligand is, you should read the
introduction to complex ions as a matter of urgency!

Use the BACK button on your browser to return to this page.

When the ligands bond with the transition metal ion, there is
repulsion between the electrons in the ligands and the electrons
in the d orbitals of the metal ion. That raises the energy of the d
orbitals.

However, because of the way the d orbitals are arranged in

space, it doesn't raise all their energies by the same amount.
Instead, it splits them into two groups.

The diagram shows the arrangement of the d electrons in a Cu2+

ion before and after six water molecules bond with it.

Whenever 6 ligands are arranged around a transition metal ion,

the d orbitals are always split into 2 groups in this way - 2 with a
higher energy than the other 3.
The size of the energy gap between them (shown by the blue
arrows on the diagram) varies with the nature of the transition
metal ion, its oxidation state (whether it is 3+ or 2+, for example),
and the nature of the ligands.

When white light is passed through a solution of this ion, some

of the energy in the light is used to promote an electron from the
lower set of orbitals into a space in the upper set.

Each wavelength of light has a particular energy associated with

it. Red light has the lowest energy in the visible region. Violet
light has the greatest energy.

Suppose that the energy gap in the d orbitals of the complex ion
corresponded to the energy of yellow light.

The yellow light would be absorbed because its energy would be

used in promoting the electron. That leaves the other colours.

Your eye would see the light passing through as a dark blue,
because blue is the complementary colour of yellow.

Warning: This is a major simplification, but is adequate for

this level (UK A level or the equivalent). It doesn't, for
example, account for absorption happening over a broad
range of wavelengths rather than a single one, or for cases
where there is more than one colour absorbed from different
parts of the spectrum.

If your syllabus wants you to know about the way the shapes
of the d orbitals determine how the energies split, then follow
this link for a brief explanation.

What about non-transition metal complex ions?

Non-transition metals don't have partly filled d orbitals. Visible

light is only absorbed if some energy from the light is used to
promote an electron over exactly the right energy gap. Non-
transition metals don't have any electron transitions which can
absorb wavelengths from visible light.
For example, although scandium is a member of the d block, its
ion (Sc3+) hasn't got any d electrons left to move around. This is
no different from an ion based on Mg2+ or Al3+. Scandium(III)
complexes are colourless because no visible light is absorbed.

In the zinc case, the 3d level is completely full - there aren't any
gaps to promote an electron in to. Zinc complexes are also
colourless.

Tetrahedral complexes

Simple tetrahedral complexes have four ligands arranged

around the central metal ion. Again the ligands have an effect on
the energy of the d electrons in the metal ion. This time, of
course, the ligands are arranged differently in space relative to
the shapes of the d orbitals.

The net effect is that when the d orbitals split into two groups,
three of them have a greater energy, and the other two a lesser
energy (the opposite of the arrangement in an octahedral
complex).

Apart from this difference of detail, the explanation for the origin
of colour in terms of the absorption of particular wavelengths of
light is exactly the same as for octahedral complexes.

The factors affecting the colour of a transition metal

complex ion

In each case we are going to choose a particular metal ion for

the centre of the complex, and change other factors. Colour
changes in a fairly haphazard way from metal to metal across a
transition series.

The nature of the ligand

Different ligands have different effects on the energies of the d

orbitals of the central ion. Some ligands have strong electrical
fields which cause a large energy gap when the d orbitals split
into two groups. Others have much weaker fields producing
much smaller gaps.

Remember that the size of the gap determines what wavelength

of light is going to get absorbed.

The list shows some common ligands. Those at the top produce
the smallest splitting; those at the bottom the largest splitting.
The greater the splitting, the more energy is needed to promote
an electron from the lower group of orbitals to the higher ones. In
terms of the colour of the light absorbed, greater energy
corresponds to shorter wavelengths.

That means that as the splitting increases, the light absorbed will
tend to shift away from the red end of the spectrum towards
orange, yellow and so on.

There is a fairly clear-cut case in copper(II) chemistry.

If you add an excess of ammonia solution to hexaaquacopper(II)

ions in solution, the pale blue (cyan) colour is replaced by a dark
inky blue as some of the water molecules in the complex ion are
replaced by ammonia.

The first complex must be absorbing red light in order to give the
complementary colour cyan. The second one must be absorbing
in the yellow region in order to give the complementary colour
dark blue.

Yellow light has a higher energy than red light. You need that
higher energy because ammonia causes more splitting of the d
orbitals than water does.

It isn't often as simple to see as this, though! Trying to sort out

what is being absorbed when you have murky colours not on the
simple colour wheel further up the page is much more of a
problem.

The diagrams show some approximate colours of some ions

based on chromium(III).

It is obvious that changing the ligand is changing the colour, but

trying to explain the colours in terms of our simple theory isn't
easy.

Note: To be honest, I spent a couple of weeks trying to find a

way of doing this simply, based on a simple colour wheel, and
eventually gave up. Life is too short!
The oxidation state of the metal

As the oxidation state of the metal increases, so also does the

amount of splitting of the d orbitals.

Changes of oxidation state therefore change the colour of the

light absorbed, and so the colour of the light you see.

Taking another example from chromium chemistry involving only

a change of oxidation state (from +2 to +3):

The 2+ ion is almost the same colour as the hexaaquacopper(II)

ion, and the 3+ ion is the hard-to-describe violet-blue-grey
colour.

The co-ordination of the ion

Splitting is greater if the ion is octahedral than if it is tetrahedral,

and therefore the colour will change with a change of co-
ordination. Unfortunately, I can't think of a single simple example
to illustrate this with!

The problem is that an ion will normally only change co-

ordination if you change the ligand - and changing the ligand will
change the colour as well. You can't isolate out the effect of the
co-ordination change.

For example, a commonly quoted case comes from cobalt(II)

chemistry, with the ions [Co(H2O)6]2+ and [CoCl4]2-.

The difference in the colours is going to be a combination of the

effect of the change of ligand, and the change of the number of
ligands.

Note: There is an interesting range of compounds described

as "thermochromic". These change colour on heating. An
example is [(CH3CH2)2NH2]2CuCl4. This contains the
tetrachlorocuprate(II) ion combined with a positive ion which
is essentially an ammonium ion where two of the hydrogens
have been replaced by ethyl groups.
 This is a bright green solid in the cold, but changes to bright
yellow at 43°C.

The bright green solid has the four chlorines arranged around
the central copper(II) ion in a square planar arrangement. The
yellow one has them arranged in a distorted tetrahedron. The
change of colour is due to the change of ligand arrangement.

This is degree level stuff. If you want to follow it up, you could
do a Google (including Google Books) search for
thermochromic tetrachlorocuprate(II).

Questions to test your understanding

If this is the first set of questions you have done, please read the
introductory page before you start. You will need to use the BACK BUTTON
on your browser to come back here afterwards.

questions on the origin of colour in complex ions

answers

Where would you like to go now?

To the complex ion menu . . .

To the Inorganic Chemistry menu . . .

To Main Menu . . .

You might also be interested in:

UV-visible spectrometry . . .

This looks at the origin of colour in organic compounds in some

detail. It has more about the electromagnetic spectrum, a description
of a UV-visible absorption spectrometer, and an explanation of how
this can be used to measure the concentrations of dilute solutions of
coloured compounds.

© Jim Clark 2003 (last modified November 2014)