MODULE CODE: NCHE 321

PRACTICAL DATE: AUGUST 2023

EXPERIMENT 4: ELECTRONIC ABSORPTION OF SOME Cu(II) COMPLEXES

Abstract:
Title: Electronic Absorption Spectra and Crystal Field Splitting Energies of Cu(II) Complexes

Introduction:

The world of transition metal chemistry is characterized by its captivating array of colors exhibited by
various compounds. These hues are not just aesthetically pleasing; they offer profound insights into the
electronic structure and behavior of transition metal complexes. The electronic absorption spectra of
these compounds, a focal point of study in this experiment, unveil the intricate energy-level transitions
that govern their vibrant colors and have far-reaching implications in both theoretical and practical
aspects of chemistry.

At the heart of understanding the electronic absorption spectra lies the Crystal Field Theory (CFT), a
theoretical framework that illuminates the interplay between transition metal ions and their
coordinating ligands. According to CFT, the interaction between the metal ion and ligands is primarily
electrostatic. This interaction induces a perturbation in the d orbitals of the metal ion, leading to the
splitting of these degenerate orbitals into distinct energy levels. This splitting is particularly pronounced
in octahedral coordination environments, where the d orbitals divide into t2g (lower energy) and eg
(higher energy) sets.

The energy difference between these sets is referred to as the crystal field splitting energy (o). This
energy gap dictates the absorption of light as electrons transition between these orbitals. In the context
of Cu(II) complexes, with a d9 electronic configuration, these transitions involve the promotion of
electrons from the lower-energy t2g orbitals to the higher-energy eg orbitals. The absorbed energy
corresponds to wavelengths within the visible region, rendering these compounds colored.

The complementary scenario is observed for a d9 electronic configuration, where the rearrangement of
electrons from (t2g)6(eg)3 to (t2g)5(eg)4 is akin to promoting a single vacant hole from the eg orbitals.
This d9 transition also yields a single absorption band, albeit with different spectral characteristics
compared to the d1 case.

It's important to note that the crystal field splitting energy (o) is not a constant and varies depending on
the nature of the ligands surrounding the transition metal ion. Different ligands induce varying degrees
of splitting in the d orbitals, leading to a diverse range of absorption spectra and colors. This variability in
ligand-induced splitting is reflected in the electrochemical series, which ranks ligands based on their
capacity to induce d orbital splitting.

The main objective of this experiment is to record electronic absorption spectra for several Cu(II)
complexes and, subsequently, determine the crystal field splitting energies associated with these
transitions. By doing so, a deeper understanding of the electronic structures of these complexes can be
achieved.

The concept of electronic absorption spectra and the underlying principles of CFT have profound
significance in both organic chemistry and practical applications. In organic chemistry, understanding the
electronic transitions occurring within transition metal complexes enhances the comprehension of
reaction mechanisms involving these compounds. By leveraging the knowledge gained from electronic
absorption spectra, chemists can make informed decisions regarding reaction conditions, reactivity, and
product formation.

In practical applications, the study of electronic absorption spectra finds use in diverse fields, from
materials science to biological research. Transition metal complexes with distinct absorption profiles are
employed as dyes, sensors, and catalysts. The insights derived from this experiment contribute to the
design of materials with tailored properties, enabling innovations in fields ranging from optoelectronics
to drug development.

Aim:

The purpose of this experiment is to record electronic absorption spectra for various Cu(II) complexes
and determine their crystal field splitting energies. By doing so, we aim to gain insights into the
electronic structures of these complexes and understand the impact of ligand interactions on their
coloration and properties.

Procedure:
- [Cu(NH3)n(H2O)6-n] Complexes:
For n=0, a 1.0 cm³ volume of 1 mol dm⁻³ Cu(NO3)₂ stock solution was diluted to 50.0 cm³ in a
volumetric flask. For n=1, 5.0 cm³ of 1 mol dm⁻³ Cu(NO3)₂ solution was mixed with 14 g of solid
ammonium nitrate. The mixture was warmed and stirred at around 30°C, followed by the
addition of 5 cm³ of 1 mol dm⁻³ NH₃. After stirring, 1.0 cm³ of this solution was diluted to 25 cm³
with 2 mol dm⁻³ NH₄NO₃ solution. Similar methods were employed for n=2 and n=3, using 2 mol
dm⁻³ NH₃ and 3 mol dm⁻³ NH₃, respectively. For n=4, 1 cm³ of concentrated NH₃ was added to 1
cm³ of 1 mol dm⁻³ Cu(NO3)₂, and the mixture was diluted to 50 cm³ with water.
- [Cu(en)₂(H2O)₂]²⁺ Complex:
A 1.0 cm³ volume of 1 mol dm⁻³ Cu(NO3)₂ solution was mixed with 5.0 cm³ of 0.4 mol dm⁻³
ethylenediamine solution in a 50 cm³ volumetric flask. The flask was then filled to the mark with
distilled water.
- [Cu(gly)₂(H2O)₂]²⁺ Complex:
A 1.0 cm³ volume of 1 mol dm⁻³ Cu(NO3)₂ solution was placed in a 50 cm³ volumetric flask. Solid
glycine was added to achieve a concentration of 0.40 mol dm⁻³. Subsequently, 20 cm³ of 0.1 mol
dm⁻³ NaOH was added, and the flask was filled to the mark with distilled water.
- Recording Spectra:
A Pye Unicam 8700 UV/VIS recording spectrophotometer was employed to record the electronic
absorption spectra. Visible spectra were recorded over the wavelength range of 900 to 600 nm,
using an absorbance scale from 0 to 1. The wavelength of maximum absorbance for each
complex was determined from the recorded spectra.
This experiment involved the preparation of Cu(II) complexes with different ligands and
coordination numbers. The electronic absorption spectra of these complexes were then
recorded using a UV/VIS spectrophotometer, providing insights into their electronic structures
and crystal field splitting energies.

Results and discussion:

While preparing the complexes, it was observed that the solution in n=4 had two layers. This was
because the concentrated NH3 has a low solubility, meaning it is not the right solution to dissolve
Cu(NO3) 2 .

Table 1: The absorbance of complex n = 0,1,2,3,4 and complex of (b) [Cu(en) 2(H2O) 2 ]2+ and (c)
[Cu(gly) 2(H2O)2]2+ over the range of 900 to 600nm.

wavelength [Cu(NH3) n(H2O) 6-n]2+ [Cu(en) 2(H2 O)2]2+ [Cu(gly) 2(H2O)2 ]2+

n=0 n=1 n=2 n=3 n=4 b c

600 0,049 0,055 0,016 0,113 0,840 0,423 0,349

650 0,065 0,076 0,025 0,118 0,792 0,222 0,371

700 0,097 0,104 0,043 0,133 0,767 0,100 0,278

750 0,144 0,136 0,061 0,140 0,680 0,039 0,165

800 0,147 0,138 0,067 0,135 0,620 0,012 0,092

850 0,151 0,138 0,064 0,123 0,661 -0,002 0,049

900 0,168 0,133 0,055 0,106 0,521 -0,008 0,025

The wavelength of maximum absorbance for each complex.

• Preparation of the complexes [Cu(NH3 ) n(H2 O) 6-n]2+

- n=0, 900nm
- n=1, 800nm and 850nm
- n=2, 800nm
- n=3, 750nm
- n=4,600nm
• Preparation of the complex [Cu(en) 2 (H2O) 2]2+
- (b), 600nm
• Preparation of the complex [Cu(gly) 2(H2O)2 ]2+
- (c), 650nm

Exercises

• The energies of the absorption bands in units of cm -1 (∆O)

- 1\600nm × 10 7 = 16666,67cm-1
- 1/650nm × 10 7 = 15384,62cm-1
- 1/700nm × 10 7 = 14285,71cm-1
- 1/750nm × 10 7 = 13333,33cm-1
- 1/800nm × 10 7 = 12500cm-1
- 1/850nm × 10 7 = 11764,71cm-1
- 1/900nm × 10 7 = 11111,11cm-1
 • The series of complexes [Cu(NH3) n(H2O) 6-n]2+ plot ∆O versus n and the comment on the results
obtained

No of moles (1/wavelength) × 107 =∆O

0 16666,67cm-1
1 15384,62cm-1
2 14285,71cm-1
3 13333,33cm-1
4 12500cm-1
5 11764,71cm-1
6 11111,11cm-1

Figure 1: Graph of ∆O versus n (series of complexes [Cu(NH3) n(H2 O) 6-n]2+)

- The above graph……………..

• The arrangement of ligands H2O, en, gly, NH3 in order of their capacity to cause d orbital splitting.
And comment on the order.
- NH3 > en > gly > H2O
- This arrangement can be explained by the characteristics of the ligands and their different
degrees of coordination. Due to its capacity to donate a single pair of electrons to the metal ion,
which causes a high repulsion between its electron cloud and the metal's d orbitals, ammonia
(NH3) is a strong field ligand. The d orbitals are significantly split apart as a result of this powerful
contact, producing a significant amount of crystal field splitting energy (∆).
- A bidentate ligand called ethylenediamine(en) has two nitrogen atoms that can donate
electrons. Bidentate coordination contributes to intermediate splitting of the d orbitals, however
its influence is less significant than that of ammonia.
- Compared to ethylenediamine and ammonia, glycine (gly), a multidentate ligand, generates less
splitting because it has fewer donor atoms. Glycine has a moderately negative impact on d
orbital splitting
- A weak field ligand like water (H2O) barely affects d orbital splitting. It has a low ability to donate
electrons, which leads to weak interactions with the metal's d orbitals and little splitting.
- In essence, the configuration reflects the ligands' capacity to affect the energy gap between the
d orbitals, which has a direct bearing on the electronic absorption spectra and colouring of the
Cu(II) complexes that have been seen. While weak field ligands provide narrower splitting and
milder hues, strong field ligands result in significant splitting and often produce more vivid
coloration.
-
Discussion:

Conclusion:

Reference: