In the Laboratory

Preparation and Thermochromic Properties of

Copper(II)-N,N-Diethylethylenediamine
Complexes
Ai-Li Cui, Xi Chen, Long Sun, Jing-Zhi Wei, Jin Yang, and Hui-Zhong Kou*
Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China
*kouhz@mail.tsinghua.edu.cn

This experiment illustrates the thermochromism of com-
pounds at the undergraduate level. Such compounds demonstrate
reversible color change upon heating or cooling. For inorganic
compounds, this transition is usually due to change in the crystal-
line phase, in coordination geometry around a metal ion, or in the
number of solvent molecules in the coordination sphere (1). Syn-
thesis of thermochromic coordination compounds of Cat2-
[MCl4] (Catþ = diethylammonium, dimethylammonium) and
M2HgI4 [M = Cu(I), Ag(I)] has been reported in this Journal (2-6).
It is noteworthy that most experiments or demonstrations deal with
transition-metal halides.
In this undergraduate laboratory experiment, the syntheses
of thermochromic chelate compounds [Cu(deen)2](NO3)2 and
[Cu(deen)2](BF4)2 (deen = N,N-diethylethylenediamine) are per-
formed (Scheme 1). The solids are stable and change color from
red to violet at transition temperature of 145 and 15 °C, respec-
tively. Such phenomena (7) can easily be observed. The red and
the violet phases for [Cu(deen)2](BF4)2 are practically isostruc-
tural to the perchlorate compound [Cu(deen)2](ClO4)2 (8, 9)
that also displays similar thermochromic behavior. Structural
determination of [Cu(deen)2](ClO4)2 shows that the red-violet
color change corresponds to the structural change of the CuN4
coordination configuration from square planar to tetrahedral
(vide post). By comparing the structures of [Cu(deen)2](ClO4)2,
students learn the origin of the thermochromic property of
[Cu(deen)2](BF4)2. The time required for the experiment is 3-4 h.
This experiment is suitable for first-year undergraduates major-
ing in chemistry.
Experimental Details
This experiment contains two parts: synthesis and thermo-
chromism tests. All chemicals are of analytical grade and are com-
mercially available. The preparation experiments are conducted in
fume hood at room temperature. The precursor Cu(BF4)2 can be
prepared in situ by reacting an excess quantity of solid cupric
carbonate basic, CuCO3 3 Cu(OH)2, with tetrafluoroboric acid
(40% in water) (10, 11). The filtrate containing Cu(BF4)2 is
subsequently used to react with N,N-diethylethylenediamine.
Preparation of [Cu(deen)2](BF4)2
An excess of CuCO3 3 Cu(OH)2 (0.830 g, 3.75 mmol) is
added with stirring to 40% aqueous HBF4 (2.2 g, ca. 10 mmol)
in a 100 mL beaker. After the releasing of CO2 has ceased,
ethanol (30 mL) is added to the solution. The unreacted solid
CuCO3 3 Cu(OH)2 in the reaction mixture is removed by filtra-
tion. To the light blue filtrate, an ethanolic solution (30 mL) of
Scheme 1. Synthesis of the [Cu(deen)2]X2 Complexes
N,N-diethylethylenediamine (1.16 g, 10 mmol) is added drop-
wise with stirring. Stirring is continued for an additional 5 min.
A violet microcrystalline solid precipitates from the solution
after standing at room temperature (28 °C) for about 5 min. The
solid is collected by suction filtration and then washed twice with
diethyl ether (5 mL) to remove any absorbed byproducts. The
solid is placed on filter paper, air-dried for 30 min, and then
weighed.
Preparation of [Cu(deen)2](NO3)2
Cu(NO3)2 3 3H2O (1.2 g, 5 mmol) is dissolved in absolute
ethanol (40 mL) in a 150 mL beaker, giving a clear blue solution.
Ethanolic solution (10 mL) of N,N-diethylethylenediamine
(1.16 g, 10 mmol) is added to the blue solution dropwise with
stirring. The color of the reaction mixture turns blue-violet.
A red solid precipitates from the solution after standing for about
10 min. The solid is collected by suction filtration, and washed
twice with diethyl ether (5 mL). The solid is placed on filter
paper, air-dried for 30 min, and then weighed.
Thermochromism of [Cu(deen)2]X2 (X = BF4-, NO3-)
The solids undergo color changes at certain temperatures
when heated or cooled. The exact transition temperature should
be determined by heating the solid using a platform-type
melting point apparatus. A small quantity, few milligrams, of
[Cu(deen)2](BF4)2 or [Cu(deen)2](NO3)2 solid are heated on a
melting point apparatus. Students record the temperatures at
which the color change occurs. Note that, if the ambient
temperature is higher than the transition temperature (∼25 °C),
that is, [Cu(deen)2](BF4)2 is in the violet form at room tem-
perature, this procedure should be omitted.
A small quantity of violet [Cu(deen)2](BF4)2 solid is placed
in a test tube. The solid is chilled in an ice water bath until the

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r 2010 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 88 No. 3 March 2011 Journal of Chemical Education 311
10.1021/ed100103a Published on Web 12/17/2010
 In the Laboratory

color change occurs. After the test tube is removed from the ice
water bath, the color reverses to the original color within a few
minutes. Alternatively, if the ambient temperature is low and
[Cu(deen)2](BF4)2 exists in the red form, the red solid can be
heated using a hair dryer or heat gun or by immersing in a hot
water bath at 80 °C. After the color change is completed, the test
tube is removed from water bath and the color is observed. The
process can be repeated many times.
A small quantity of red [Cu(deen)2](NO3)2 is placed in a
test tube. The test tube is heated in an oven at 146 °C for 3-
5 min. The test tube is removed and the violet color is observed.
The solid is allowed to cool on the bench, but the violet color
remains as the transition to the red color takes nearly 2 months at
room temperature.
Figure 1. The color change of [Cu(deen)2](BF4)2 (upper) and [Cu(deen)2]-
Hazards (NO3)2 (lower).

The diamine is corrosive and causes irritation to skin and

eyes. Breathing diamine will cause coughing and short breath and
may damage the lungs. It is harmful if inhaled or in contact with
skin. HBF4 is harmful by inhalation, in contact with skin, or
swallowed. Copper nitrate is a strong oxidizer and causes irritation
to the eyes, skin, and respiratory tract. CuCO3 3 Cu(OH)2 causes
irritation to the eyes, skin, and respiratory tract. Ethanol and
diethyl ether are flammable and harmful if inhaled or absorbed Figure 2. The different coordination configuration of Cu(II) in [Cu(deen)2]-
through skin. (BF4)2: the structure on the left is the red form and the structure on the right is
the violet form.

Results and Discussion whereas it takes nearly 2 months for the violet nitrate compound
to turn red.
Bidentate diamine ligands can coordinate to transition-metal
ions in a chelating mode to form stable [M(L)x]nþ (x = 1-3)
Acknowledgment
species. In the case of N,N-diethylethylenediamine, reaction with
CuX2 (X- = NO3-; BF4-) in a molar ratio of 2:1 gives rise to We acknowledge the financial support from the National
compounds [Cu(deen)2]X2. The reaction can be performed at Natural Science Foundation of China (20953006) and Ministry of
room temperature in a nonaqueous solution, for example, ethanol. Science Technology, China through 973-project (2002CB613301).
The synthesis is simple, and students can learn a nonaqueous syn- We thank Joseph F. Chiang (State University of New York) for
thetic method for the preparation of coordination compounds, proof reading the English language of this manuscript.
especially the use of appropriate solvents to isolate the products. The
use of ethanol is crucial for the preparation, and the volume of the Literature Cited
solvent used can significantly affect the yield of the products. It is
suggested that this effect should be investigated in the lab during the 1. Day, J. H. Chem. Rev. 1988, 68, 649.
preparation of the tetraborate compound. 2. Van Oort, M. J. M. J. Chem. Educ. 1988, 65, 84.
Both solids show thermochromic properties where they 3. Hughes, J. G. J. Chem. Educ. 1998, 75, 57.
change color from red to violet (Figure 1). The transition 4. Chen, C.; Zhou, Z.; Zhou, Y.; Du., J. J. Chem. Educ. 2000, 77, 1206.
temperatures of [Cu(deen)2](BF4)2 and [Cu(deen)2](NO3)2 5. Choi, S.; Larrabee, J. A. J. Chem. Educ. 1989, 66, 774.
occur at 15 and 145 °C, respectively. Because of the low transi- 6. Bukleski, M.; Petrusevski, V. M. J. Chem. Educ. 2009, 86, 30.
tion temperature of the tetrafluoroborate compound, the isolated 7. Fabbrizzi, L.; Michcloni, M.; Paoletti, P. Inorg. Chem. 1974, 13,
solid may be violet or red in color depending on the ambient 3019.
temperature. Structural analysis of the isostructural [Cu(deen)2]- 8. Grenthe, I.; Paoletti, P.; Sandstrom, M.; Glikberg, S. Inorg. Chem.
(ClO4)2 shows that subtle structural variation is responsible for 1979, 18, 2687.
the color change (8). At low temperature, the Cu(II) coordina- 9. Naumov, P.; Sakurai, K.; Asaka, T.; Belik, A. A.; Adachi, S.-i.;
tion geometry can be described as ideal planarity with four Takahashi, J.; Koshihara, S.-y. Inorg. Chem. 2006, 45, 5027.
nitrogen atoms of the two coordinating deen ligands in a square 10. Narayanan, B.; Bhadbhade, M. M. J. Coord. Chem. 1998, 46, 115.
planar arrangement. At high temperature, the CuN4 coordina- 11. Lever, A. B. P.; Mantovani, E.; Donini, J. C. Inorg. Chem. 1971, 10,
tion plane slightly deviates from planarity with the distortion of 2424.
backbone alkyl groups in N,N-diethylethylenediamine (Figure 2).
However, the very weak axial coordination contributes little to Supporting Information Available
the color change. The reversibility of thermochromic property Lab Documentation containing experimental procedure for the
for the two compounds is different. The red tetrafluoroborate students, student handouts and instructor notes. This material is
reverses to the violet form in 1 min when warmed on the bench, available via the Internet at http://pubs.acs.org.

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312 Journal of Chemical Education Vol. 88 No. 3 March 2011 pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.