Pyrene Excimer Formation Kinetics

October 19, 2016

Tanya Daher
Partners: Paul Blanchard, Devon Diehl, Andrew Draskovics
Department of Chemistry, The Pennsylvania State University, University Park,
PA, 16802
CHEM 457, Section 4, Fall 2016

1. Abstract
In this experiment, we determined the luminescent properties of pyrene
using fluorimetry. With an exploration between two parallel and two
consecutive reactions, the kinetic rate constants were found. Using timeresolved laser photolysis, the rate constants for the pyrene excimer
formation were also found to be ko = 0.1817, k1 = 3x109 k-1 is negligible and
k2 is 2.3x107.\
2. Introduction
In this laboratory, the excited state of pyrene (*Py) and its excimer (*Ex)
were analyzed. An excimer is an excited state dimer combining the singlet
excited state reacting with the ground state molecule.
Py + hv *Py (excitation)
*Py Py + hvM (singlet pyrene decay accompanied with fluorescence)

Pyrene can be used to produce dyes due to its high quantum yield and
long lifetime. To create the excimer of pyrene, the UV light will excite
pyrene (Py) from its ground state to a singlet excited state (*Py).
*Py + Py

*Ex (excimer formation)

*Ex 2Py + hvE (excimer decay accompanied with fluorescence)

Emission spectrums are produced to relate the different concentrations of

pyrene to discover luminescent species. Interference filters can be used to
see (*Py) and (*Ex) separately. With a low concentrated solution, the
transition from the ground state to the excited state is quit visible. The
rate constants ko and k2 can be found and include nonradiative decay
mechanisms. Py and *Py will not react in dilute solutions if the reactants
do not encounter each other within the lifetime of their excited states
(they usually do not). In concentrated solutions, the collision frequency is
high enough to absorb at 337 nm. This reaction crates a concentration
gradient of *Py within the molecule. To identify a different wavelength, the
absorption spectrum of the concentrated pyrene solution can be used.

The first order decay of *Py fluorescence to the ground state is described
by ko. The second order rate constant for the formation of *Ex is k1 and
the first-order rate constant for the dissociated of *Ex to Py and *Py is k-1.
For *Ex, the fluorescence decay rate constant is k2.

The rate equations that describe the time-dependent concentrations of

*Py and *Ex are:
d [ Py ]
=( k o + k 1 [ Py ] ) [ Py ]
dt
d [ Ex ]
=( k 2 ) [ Ex ] +k 1 [ Py ] [ Py }
dt

3. Experimental
In this experiment, the Horiba Scientific Fluorolog FL-3 spectrofluorimeter
was used to determine the reaction rate constants for pyrene excimer
formation. Five samples were tested that contained luminescence decays
of nitrogen-purged 10 M, 0.01 mM, 0.5 mM, 1.0 mM, and 1.5 mM
solutions. These solutions were previously prepared by using 2 mM pyrene
and diluting it. An absorption spectrum was taken of each pyrene solution
between the wavelengths of 300 and 400 nm. The optical density at 337.1
and 366 nm from the absorption spectrum is 334.555 nm.
An emission spectrum was then taken of each pyrene solution using an
emission scan of wavelength 337.1 nm for the 10 M solution and 366 for
the other samples. The emission scan range was between 350 and 500
nm for the 10 M solution and for the other samples it was between 375

and 700 nm to accommodate the 366 nm wavelength signal. Figure 1

displays the set up to observe the emission spectrum.

Figure 1. Laser Photolysis setup.

A luminescence decay of the five samples of concentrations of pyrene were
taken within two different filters. The two filters have wavelength of 400 nm
and 500 nm. The luminescence decay was taken with a laser pulse at
excitation wavelength of 337.1 nm and for the 10 M solution it was taken
with an excitation wavelength of 366 nm.

4. Results and Discussion

10 microM

0.01 mM

0.5 mM

1.0 mM

1.5 mM

The absorption spectra of the samples were taken and observed to have
excitation wavelengths at 337 nm and 366 nm.
Figure 1. UV spectra of Wavelengths and Absorbances
Within the graph, one can clearly identify an excitation peak at
wavelength 337 nm and also at 366 nm. The pink line depicts the 10 M
solution that is absorbed at a very low absorbance rate due to its low
concentration of pyrene. The rest of the samples are depicted with an
absorbance between 2 and 3.5. The 10 M solution is depicted well at 337
nm but the other samples are not. To take this spectrum, we cannot use a

wavelength of 337 nm because the absorbance for a higher concentration of

pyrene is too high. Thus, for a higher concentration of pyrene, a higher
wavelength is favored, such as 366 nm.
1.2

0.8

Emission Intensity

0.6

0.4

0.2

Figure 2. Normalized Emission Spectra

Within Figure 2, the variety of sampled concentrations are depicted within
specific ratios of each other. This plot represents the normalized content of
the wavelength and absorbance. The second highest peak had a value of
381.75 nm and was represented to be our normalized point. This peak is a
result by the 0.01 nm concentration of pyrene. The increase in the intensity
of excimer fluorescence on increasing the pyrene concentration indicates
that the pyrene ground state is involved in excimer formation. All of the
different concentrations were read at this point which allows us to assume
that 366 nm is the objective wavelength for these solutions.

f(x) = 0.18 exp( -2773234.66 x )

R = 1

Figure 3. Emission spectrum/luminescence decay of pyrene

In figure 3, the concentrations of pyrene were plotted including, 10 M, 0.01
mM, 0.5 mM. 1.0 mM and 1.5 mM. Looking at the image below (on the left),
one can also see that the concentrated solutions of pyrene are shown using a
laser at wavelength of 337 nm. The picture on the right shows the
wavelength of 366 nm not capturing the emission of the concentration.

f(x) = NaN exp( NaN x )

R = NaN

f(x) = 0.82 exp( -6504809.11 x )

f(x)
0.77 exp( -7591526.27 x )
R ==0.99
R = 0.99

Time (s)
N 0.01 mM

Exponential (N 0.01 mM)

N 0.5 mM

Exponential (N 0.5 mM)

N 1.0 mM

Exponential (N 1.0 mM)

N 1.5 mM

Exponential (N 1.5 mM)

N 0.01 mM

N 0.5 mM

N 1.0 mM

N 1.5 mM

Figure 4. Luminescence decay of pyrene

Figure 5. Normalized luminescence decay of pyrene

In figure 4, the luminescence decay of pyrene is depicted with four different

pyrene concentrations plotted. The four concentrations decay in different
times and the concentration of 1.5 nM is has the fastest decay time of
pyrene. These decays are taken with a 400 nm filter.
Figure 5 is the normalized graph of the luminescence decay of pyrene. The
natural logs are plotted and it describes the pyrene monomer with single
exponential fits over a range of concentrations. An exponential fit was taken
for every concentration and the slope of them depicts the kobs per
concentration of pyrene. Table 1 depicts the concentrations with the Kobs.

Table 1. Concentration of pyrene vs kobs

Concentration of

kobs

kobs

0.00001

2771577.2

1346.4437

0.0005

3
4527663.4

4
5147.7889

0.001

6504809.1

2
8949.326

0.0015

1
7591526.2

10855.465

Pyrene (M)

f(x) = 3306256736.94x + 2860935.81

R = 0.99

Figure 6. linear plot of kobs vs concentration of pyrene

In figure 6, the kobs values of the exponential decay are compared to the
concentration of pyrene to depict the linear relationship between the two
measurements. The pseudo-first order kinetics is obeyed. The k1 value is
determined from the slope and the value of it is 3x109. This slope allows us
to conclude that the decay of pyrene is evolved in a positive linear formation.
The value of k-1 is negligible while comparing it to the other rate constants at
room temperature. While taking a look at the emission spectrum of pyrene,
figure 4 and figure 5 can both show that energy is required to go through k-1
but the decay is releasing energy, therefore its negligible. You cannot have a
rate constant that is negative because there is no such thing as negative
time.

-1.00E-07

4.00E-07

9.00E-07

Time (s)
0.5 mM

1.0 mM

1.5 mM

Figure 7. Emission Spectrum

The laser that was used in the basement of Davey, is depicted in figure 7.
This is the emission spectrum of the concentrated pyrene samples with a
500 nm filter on top. The laser is fast enough to monitor excimer formation.
It is important to have an approximately homogenous distribution of excited
state pyrene molecules when performing laser photolysis to study the
kinetics of the system. This is important because experimentally sampling
different concentrations of pyrene allows one to make concise observations
of wavelengths/absorbance jumps between ground states and excited states.
With higher concentrations, there is much more of a buildup among the
absorbance rates and this does not happen instantaneously. The ground
state is slow to find an excited state. An excited state finds ground quicker.
The image that is below, represents the laser photon emitted using a 366 nm
wavelength on a stronger laser.

5. References
1. Birks, J. B. Photophysics of Aromatic Molecules; Wiley-Interscience:
London, 1970.
2. Platt, J. R. J. Chem. Phys. 1949, 17, 484-495.
3. Hanlon A.D. and Milosavljevic B.H., Photochem. Photobiol. Sci., 12 (5),
787-797 (2013)
4. Hanlon A.D. and Milosavljevic B.H. J. Lumin., 157, 16-20 (2015)

6. Conclusion
The contents of the experiment include determination of luminescent
properties of a specific chemical compound, pyrene. To determine the
luminescent properties, we used methods of fluorimetry through lasers.
Using time-resolved laser photolysis helped us conclude the rate
constants of the pyrene excimer formation. The rate constants include, ko
= 0.1817, k1 = 3x109, k-1 is negligible and k2 is 2.3x107. These rate
constants helped us conclude the times that dfferent concentrated pyrene

excimers can be formed through photolysis. This also helped us conclude

that within a specific time lapse, different wavelengths affect the speed of
luminescent decay. A 366 nm wavelength is an ideal wavelength to use.