Chemiluminescence during decomposition of 1,4-dimethylnaphthalene endoperoxide on the silica gel and alumina surface

Article abstract of DOI:10.1007/s11172-007-0034-z

Decomposition of 1,4-dimethylnaphthalene endoperoxide supported on the silica gel and alumina surface is accompanied by chemiluminescence (CL) in the IR and visible spectral regions. The CL emitter in the IR region is singlet oxygen. The ¹O₂ dimol contributes mainly to the emission at λ_max = 630 and 700 nm. It was shown by the IR-CL method that endoperoxide decomposition on the sorbent surface follows the first-order kinetics. The activation parameters of the process were determined. On the Al₂O₃ and silica gel surfaces a substantial acceleration of the decomposition of 1,4-dimethylnaphthalene endoperoxide is observed compared to the solution.

Full text of DOI:10.1007/s11172-007-0034-z

Russian Chemical Bulletin, International Edition, Vol. 56, No. 2, pp. 205—210, February, 2007
205
Chemiluminescence during decomposition of 1,4ꢀdimethylnaphthalene
endoperoxide on the silica gel and alumina surface
D. V. Kazakov,aꢀ D. V. Mal´tsev,a G. Ya. Maistrenko,a S. L. Khursan,b M. Yu. Ovchinnikov,b and V. P. Kazakova
aInstitute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences,
71 prosp. Oktyabrya, 450054 Ufa, Russian Federation.
Fax: +7 (347 2) 35 6066. Eꢀmail: chemlum@anrb.ru; dmitri_kazakov@mail.ru
bDepartment of Chemistry, Bashkir State University,
32 ul. Frunze, 450007 Ufa, Russian Federation.
Fax: +7 (347 2) 33 1677
Decomposition of 1,4ꢀdimethylnaphthalene endoperoxide supported on the silica gel and
alumina surface is accompanied by chemiluminescence (CL) in the IR and visible spectral
regions. The CL emitter in the IR region is singlet oxygen. The 1O2 dimol contributes mainly to
the emission at λmax = 630 and 700 nm. It was shown by the IRꢀCL method that endoperoxide
decomposition on the sorbent surface follows the firstꢀorder kinetics. The activation paramꢀ
eters of the process were determined. On the Al2O3 and silica gel surfaces a substantial accelꢀ
eration of the decomposition of 1,4ꢀdimethylnaphthalene endoperoxide is observed compared
to the solution.
Key words: chemiluminescence, singlet oxygen, endoperoxides, alumina, silica gel.
Singlet oxygen 1О2 plays an important role in organic
synthesis, biochemistry, and medicine and evokes conꢀ
stant interest for investigation of chemiꢀ and bioluminesꢀ
cence.1—8 Reactions of hydrogen peroxide with ClO– and
metals (e.g., MoO42–) and decomposition of peroxy comꢀ
plexes and trioxides are most frequently used for the
chemical generation of singlet oxygen.1 Along with these
processes, the thermal decomposition of endoperoxides
accompanied by a high yield of excited oxygen generation
is widely used.7,8 Endoperoxides are rather inert, which
makes it possible to avoid side oxidation reactions when
they are used as sources of singlet oxygen in organic synꢀ
thesis. In addition, endoperoxides are relatively stable at
room temperature compared, i.e., with trioxides,9 and
a rather wide set of the presently synthesized derivatives
allows one to study the properties of this class of comꢀ
pounds in both organic and aqueous media.7,8 Remarkꢀ
ably, in the case of endoperoxides, the formation of the
singlet state (1О2) is a result of the simple monomolecular
reaction of peroxide decomposition to the initial hydroꢀ
carbon and oxygen (Scheme 1), which makes these comꢀ
pounds to be a good model for studying the elementary
act of chemiexcitation.
Many works (see reviews7,8) are devoted to the study
of various aspects of chemical transformations of endoꢀ
1
peroxides in solutions (yields of О2, products, mechaꢀ
nism, and kinetics of decomposition). Data concerning
the behavior of endoperoxides on the solid surface are
lacking. At the same time, it is known that the decompoꢀ
sition of peroxy compounds can considerably be accelerꢀ
ated on the surface, which, in addition, sometimes affects
the processes affording products in the electronꢀexcited
state.10 In addition, data on stability of endoperoxides
can be helpful when using these compounds as sources of
singlet oxygen for oxidation on a solid support.
Therefore, in the present work 1,4ꢀdimethylnaphthaꢀ
lene endoperoxide (MNEP) was used as an example to
study the behavior of endoperoxides sorbed on the aluꢀ
mina and silica gel surface.
Experimental
Synthesis of MNEP was carried out according to a described
procedure11,12 but with insignificant modifications.
A glass reactor cooled to 0 °С was loaded with CH2Cl2
(18 mL), freshly distilled 1,4ꢀdimethylnaphthalene (1 mL, ~1 g),
and methylene blue (2 mg) dissolved in CH2Cl2 (1 mL). The
reaction was carried out with continuous oxygen purging and
irradiation with a DKSSh xenon lamp (1000 W) through the
light filter with the transmission wavelength >500 nm to prevent
the photodestruction of MNEP that formed. After ~30 h the
synthesis was stopped, and the solution was passed through
a column with neutral alumina (l = 10 cm, d = 3.5 cm) to
Scheme 1
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 199—204, February, 2007.
1066ꢀ5285/07/5602ꢀ0205 © 2007 Springer Science+Business Media, Inc.

206
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 2, February, 2007
Kazakov et al.
remove methylene blue (waterꢀjet pump was used for faster passꢀ
ing the solution through Al2O3). Some portion of the endoperꢀ
oxide was sorbed on the column and washed with a new portion
of CH2Cl2. Then CH2Cl2 was removed in vacuo, and the mixꢀ
ture of unreacted 1,4ꢀdimethylnaphthalene and its endoperoxide
was repeatedly recrystallized from a heptane—CH2Cl2 (10 : 1)
mixture at 0 °С. As a result, a white crystalline powder of the
endoperoxide (~200 mg) was obtained and stored in the dark
at –20 °C.
S•10–2 (rel. units)
500
400
300
200
100
1,4ꢀDimethylnaphthalene endoperoxide was identified usꢀ
1
ing Н NMR on a Bruker AM 300 spectrometer (300 MHz) by
the characteristic signal11 of protons of the methyl group in the
endoperoxide at δ 1.85 in CDCl3 (signals of other protons, δ:
6.70 (s, 2 H); 7.21, 7.29 (both dd, 1 H each, J = 7.4 Hz, J =
7.5 Hz); 7.33, 7.40 (both d, 1 H each, J = 7.5 Hz)).
0
10
20
30
[MNEP]•105/mol g–1
Quantitative analysis of the endoperoxide was carried out by
1Н NMR in CDCl3 using acetone as the standard. Purity of the
product was 100%.
The sorbent surface was modified by MNEP as follows.
A solution (0.5 mL) of the endoperoxide in CCl4 was added to
silica gel or Al2O3 (0.1 g) at 0 °C. The suspension was stirred,
and the solvent was removed in vacuo.
Fig. 1. Plot of the total IRꢀCL intensity (S) arising upon the
MNEP decomposition at 70 °С on neutral alumina vs. amount
of the supported endoperoxide.
Results and Discussion
Carbon tetrachloride was purified and dried using a known
procedure.13 1,4ꢀDimethylnaphthalene was purified by vacuum
distillation. 1,4ꢀDiazabicyclo[2.2.2]octane (DABCO) was reꢀ
peatedly recrystallized from bidistilled water.
Silica gel with a surface area of 600 m2 g–1 and a particle size
of 0.125—0.160 mm, 0.160—0.200 mm, or 7.5 µm and acidic,
neutral, and basic silica were used. Silica gel and Al2O3 were
calcined prior to use for 3 h at 150 °С. In all entries, a weighed
sample of alumina and silica gel was 100 mg.
Chemiluminescence in the IR spectral range. Thermolyꢀ
sis of MNEP on the silica gel and alumina surface is acꢀ
companied by CL in the IR spectral range (λ > 1000 nm).
As can be seen from the data in Fig. 1, the total IRꢀCL
intensity (S) is proportional to the concentration of enꢀ
doperoxide supported on the Al2O3 surface (similar data
were obtained on silica gel). Evidently, as in solution,1
singlet oxygen is the light emitter on the surface in the
IR range (Scheme 2).
Chemiluminescence (CL) in the IR spectral region was deꢀ
tected on a setup described earlier10 using a FEUꢀ83 photoꢀ
multiplier tube sensitive in the IR range and cooled to –60 °C.
The range of singlet oxygen emission was picked out using the
IKSꢀ7 boundary light filter (λ = 1000—1300 nm). Chemilumiꢀ
nescence in the visible spectral range arising during MNEP deꢀ
composition was detected on a setup equipped with a FEUꢀ119
photomultiplier tube sensitive in the visible spectral range
(λ from 330 to 750 nm). The CL spectrum was obtained using
boundary light filters placed in a holder between the bottom of
the temperatureꢀcontrolled cell containing a sample and the
photocathode of the FEU tube under the following conditions:
60 °C, [MNEP] = 1•10–4 mol g–1 (on silica gel) and [MNEP] =
2•10–4 mol g–1 (on Al2O3). In particular entries, CL was deꢀ
tected through the interference light filter (λ = 700 nm) at 70 (on
silica gel) and 80 °С (on Al2O3).
Quantum chemical calculations were performed using the
Gaussian 98, Revision A.7 program.14 The structures of MNEP
and its decomposition products were determined by the comꢀ
plete optimization of geometric parameters of molecules. When
the thermal effect of MNEP decomposition was calculated, the
electron correlation energy was taken into account in the frameꢀ
work of the density functional theory (DFT). The Becke threeꢀ
parameter hybrid functional15 was used in combination with the
Lee—Yang—Parr correlation functional.16 The tripleꢀvalenceꢀ
split basis set including sets of polarization functions of the
dꢀ and pꢀtypes was used to construct molecular orbitals; thus,
the B3LYP/6ꢀ311G(d,p) approximation was used. The ∆H° value
was determined using the total energies of participants of the
reaction.
Scheme 2
1
An additional argument in favor of О2 formation is a
considerable weakening of the IRꢀCL intensity in the
presence of DABCO, which is a known quencher17 of 1О2
luminescence when supporting on both the Al2O3 and
silica gel surfaces. For instance, in the presence of DABCO
supported on silica gel ([DABCO] = 2.7•10–4 mol g–1
;
silica gel 600 m2 g–1, 0.125—0.160 mm), the total IRꢀCL
intensity upon endoperoxide decomposition (5•10–5
mol g–1) at 60 °С is by 2.7 times lower than that in the
absence of DABCO. The quenching effect on alumina is
more considerable: in the presence of even 1•10–4 mol g–1
DABCO supported on acidic Al2O3, the IRꢀCL signal for
the MNEP decomposition (1•10–4 mol g–1) at 60 °С is
not observed at all.

Chemiluminescence in endoperoxide destruction
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 2, February, 2007
207
I (rel. units)
logk
–1
300
250
200
150
100
50
–2
–3
2.8
2.9
3.0
T –1•103/K–1
Fig. 4. Temperature plot of the rate constant of MNEP decomꢀ
position (k) on silica gel ([MNEP] = 1•10–4 mol g–1; silica gel
0.160—0.200 mm, 600 m2 g–1).
0
50
100
150
t/s
Fig. 2. Typical kinetic curve of singlet oxygen IRꢀCL decay on
the silica gel surface upon the MNEP decomposition (90 °C;
[MNEP] = 1•10–4 mol g–1; silica gel 0.160—0.200 mm,
600 m2 g–1).
Table 1. Rate constants of the MNEP consumption (k) on silica
gel (0.125—0.160 mm, 600 m2 g–1) and neutral alumina at 70 °C
Silica gel
Alumina
[MNEP]•105
/mol g–1
k•103
/s–1
[MNEP]•104
/mol g–1
k•103
/s–1
lnI
6
5
4
3
2
1
1
4
7
10
50
13.1
12.6
14.9
13.3
13.8
1
4
7
10
50
10.1
10.5
7.6
12.1
11.5
the firstꢀorder law (Fig. 3). The rate constant found from
the semilogarithmic anamorphoses of the kinetic curves
of IRꢀCL decay is independent of the amount of the
endoperoxide supported on Al2O3 and silica gel (Table 1).
The temperature dependence of the rate constant of
MNEP decomposition on the silica gel and alumina surꢀ
face was studied. The plot of logk vs. 1/Т obtained on
silica gel is shown in Fig. 4. The activation energies (Ea)
and preꢀexponential factors (logA) for the endoperoxide
decomposition were determined by the temperature plots.
As can be seen from the data in Table 2, the activation
parameters of the process are virtually independent of the
properties of the silica gel surface, whereas they are lower
than those on Al2O3, except for the parameters for basic
alumina, where the Eа and logA values are close to those
obtained on silica gel. Comparison of the obtained results
(see Table 2) with published data12 on the MNEP decomꢀ
100
140
180
220 t/s
Fig. 3. Semilogarithmic anamorphosis of the kinetic curve of
IRꢀCL decay upon the MNEP decomposition on the silica
gel surface (90 °C; [MNEP] = 1•10–4 mol g–1; silica gel
0.160—0.200 mm, 600 m2 g–1).
The time dependence of the IRꢀCL intensity arising
upon the MNEP decomposition on the silica gel surface
is presented in Fig. 2. The kinetics of IRꢀCL decay upon
the MNEP decomposition on the alumina surface is simiꢀ
lar. As can be seen from the data presented in Fig. 2, the
curve passes through the maximum caused by heating of
the endoperoxide to the required temperature. The region
of the curve after the maximum reflects the decomposiꢀ
tion of the endoperoxide on the sorbent surface obeying
Table 2. Activation parameters (Ea and logA) of the MNEP decomposition on the silica gel and
alumina surfaces ([MNEP] = 1•10–4 mol g–1)*
Silica gel**
Eа
logA
Alumina
Ea
logA
/kcal mol–1
/kcal mol–1
0.125—0.160 mm
0.160—0.200 mm
7.5 µm
14.5
13.6
12.6
7.3
6.8
6.1
Acidic
Neutral
Basic
17.4
16.3
13.0
9.0
8.4
6.3
* Measurements were carried out in the 50—90 °C interval.
** The particle size is indicated. In all cases, the surface area was 600 m2 g–1
.

208
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 2, February, 2007
Kazakov et al.
logA
I (rel. units)
0.20
0.15
0.10
9
8
7
6
500
550
600
λ/nm
13
14
15
16
Ea/kcal mol–1
Fig. 6. Chemiluminescence spectrum appeared upon the
MNEP decomposition on the acidic alumina surface at 60 °C
([MNEP] = 2•10–4 mol g–1).
Fig. 5. Plot of logA vs. activation energy (Ea) of the MNEP
decomposition on the silica gel and alumina surfaces ([MNEP] =
1•10–4 mol g–1). The Ea and logA values are given by the data in
Table 2.
the emission in the visible spectral range. The CL specꢀ
trum in the MNEP decomposition on both neutral and
acidic alumina (Fig. 6) recorded using the boundary light
filters is rather complicated with emission maxima at λ =
500—540, 560—600, and 600—650 nm. The CL spectrum
appeared upon the endoperoxide decomposition on silica
gel (0.125—0.160 mm, 600 m2 g–1) is similar with the
only difference that it contains a weak emission band at
λ = 450—500 nm. In addition, the decomposition of the
endoperoxide on both Al2O3 and silica gel is accompaꢀ
nied by the emission through the interference filter at λ =
700 nm.
position in solution (Ea = 24.8 kcal mol–1, logA = 13.7,
solvent 1,4ꢀdioxane) shows that the silica gel and Al2O3
surfaces substantially catalyze the decomposition of endoꢀ
peroxide.
It should be mentioned that the activation parameters
of endoperoxide decomposition obtained by the IRꢀCL
method on different surfaces obey the compensation relaꢀ
tionship logA = 0.6Ea – 1.5 (r = 0.99) (Fig. 5), which is
characteristic of heterogeneous reactions and also of oneꢀ
act processes of temperature quenching of luminescence
of both organic compounds18 and lanthanide ions.19
It is known1,10,20 that the sum of the enthalpy (∆H°)
and activation energy of the reaction should be higher
or at least equal to the energy of the electronꢀexcited state
of the process for the excited state to be formed in
the chemical reaction. Our DFT calculations showed
that the MNEP decomposition is exothermic: ∆H° =
–17 kcal mol–1. Thus, the sum of the activation energy of
endoperoxide decomposition (13—17 kcal mol–1, see
Table 2) and ∆H° is more than enough for the transition
of oxygen to the excited 1∆g state, which lies2 at a level of
22.5 kcal mol–1. It is of interest that, according to experiꢀ
mental data,12 the decomposition of crystalline polyꢀ
aromatic 1,4ꢀendoperoxides is an endothermic reaction
(∆H° = +2—9 kcal mol–1). In authors´ opinion,12 triplet
oxygen is excited exclusively due to the activation energy.
We believe that the experimentally measured enthalpy of
the reaction12 is, in fact, the value including thermal efꢀ
fects related to the deformation and destruction of endoꢀ
peroxide crystals along with the decomposition of the
endoperoxide itself (which is exothermic in fact). If the
MNEP decomposition is endothermic, at least no chemiꢀ
luminescence of singlet oxygen would be observed on
silica gel and alumina, because only the activation energy
of the process (13—17 kcal mol–1) is not enough for
1О2 formation.
It can be assumed that the maxima at λ = 560—600
and 600—650 nm, as well as the luminescence at λ =
700 nm, are caused by radiative transitions1,21 in a molꢀ
ecule of singlet oxygen dimol (1О2)2
–
–
–
–
–
–
(1∆ )ν=1(1∆ )ν=0 → (3Σ
)
)
)
ν=0(3Σ
ν=0(3Σ
ν=1(3Σ
)
)
)
ν=0 (λmax = 578 nm),
g
g
g
g
g
g
g
g
(1∆ )ν=0(1∆ )ν=0 → (3Σ
(λ
(λ
= 633 nm),
=703 nm).
g
g
ν=0
ν=0
max
max
(1∆ )ν=0(1∆ )ν=0 → (3Σ
g
g
Note that the CL of singlet oxygen dimol upon the
MNEP decomposition in solution has been reported earꢀ
lier.22—24 The formation of (1О2)2 on the solid surface is
also favored by the fact of luminescence weakening in the
visible spectral range in the presence of the DABCO supꢀ
ported on the surface. For instance, the total CL intensity
of MNEP decomposition (1•10–4 mol g–1) at 60 °С on
the surface of acidic Al2O3 at λ > 600 nm in the presence
of 1•10–4 and 2•10–4 mol g–1 DABCO is lower by 3 and
5 times, respectively, than that in the absence of DABCO.
Similar effect of quenching of the CL intensity is obꢀ
served on silica gel: the ratio of the total CL intensities
(λ > 620 nm) upon the endoperoxide decomposition
(5•10–5 mol g–1) at 60 °С on silica gel (0.125—0.160 mm,
600 m2 g–1) in the absence and presence of DABCO
(2.7•10–4 mol g–1) is 1.54.
Chemiluminescence in the visible spectral range. In adꢀ
dition to IRꢀCL, the decomposition of the endoperoxide
on the silica gel and alumina surface is accompanied by
An additional argument in favor of dimol formation is
the effect of oxygen on the CL intensity at λ = 700 nm. It
is known from literature data25 on the photosensitized

Chemiluminescence in endoperoxide destruction
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 2, February, 2007
209
1О2 generation that in solution triplet oxygen quenches
the dimol luminescence at λ = 700 nm. According to our
data on the endoperoxide decomposition (70 °С) on the
silica gel surface (0.125—0.160 mm, 600 m2 g–1), the toꢀ
tal chemiluminescence intensity at λ = 700 nm in an
oxygen atmosphere is by 1.2 times lower than that in
argon, whereas the ratio of the total IRꢀCL intensities of
singlet oxygen is virtually the same in O2 and argon.
Remarkably, for the MNEP decomposition on both
silica gel and alumina the ratios of the total intensities of
chemiluminescence arising in the IR spectral range and at
λ = 700 nm (taking into account the spectral sensitivity
of the FEU tube) differ insignificantly and range
within 460—590. For instance, when 1•10–4 mol g–1
endoperoxide decomposes on silica gel (0.125—0.160 mm,
600 m2 g–1) SIRꢀCL/Sλ=700 = 570 (70 °С), 590 (80 °С),
and 530 (90 °С), and for the MNEP concentration
equal to 5•10–4 mol g–1 on silica gel (0.160—0.200 mm,
600 m2 g–1) SIRꢀCL/Sλ=700 is 470 (70 °С). Similar
SIRꢀCL/Sλ=700 value (464) was obtained on acidic alumina
([MNEP] = 1•10–4 mol g–1, 80 °С). This fact additionꢀ
ally evidences that the light emitter at λ = 700 nm on
silica gel and Al2O3 has the single nature. The considerꢀ
ably lower CL intensity in the visible spectral range comꢀ
pared to the IRꢀCL intensity is caused by the very low
stationary concentration of (1О2)2, which is due to the
high constant of its dissociation (1010—1011 s–1).25—28
Nevertheless, singlet oxygen dimol is not, most likely,
the only emitter in the visible spectral range. Indeed, the
results presented above show that in the IR spectral reꢀ
tion of the endoperoxide on the sorbent surface obeys the
firstꢀorder law. The activation parameters of the process
determined show that the surface substantially catalyzes
the endoperoxide decomposition compared to the proꢀ
cess in solution. In addition to IRꢀCL, the endoperoxide
thermolysis is accompanied by chemiluminescence in the
visible spectral region. It is assumed that singlet oxygen
dimol (1О2)2 contributes substantially to the CL at λmax
=
630 and 700 nm.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 05ꢀ03ꢀ
32663a), the Council on Grants of the President of the
Russian Federation (Program of State Support for Leadꢀ
ing Scientific Schools of the Russian Federation, Grant
NShꢀ5486.2006.3), and the Division of Chemistry and
Materials Science of the Russian Academy of Sciences
(Program of Fundamental Research "Theoretical and Exꢀ
perimental Investigation of the Chemical Bond Nature
and Mechanisms of the Most Important Chemical Reacꢀ
tions and Processes").
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1
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1
cause it is not detected by Н NMR. At the same time, it
cannot be ruled out that, unlike solution, the sorbent
surface provides other routes of endoperoxide decompoꢀ
sition in addition to the reaction shown in Scheme 2.
These routes are responsible for the chemiluminescence
observed at λ < 560 nm.
Thus, it is shown in the present work that the decomꢀ
position of 1,4ꢀdimethylnaphthalene endoperoxide supꢀ
ported on the silica gel or alumina surface is accompanied
by chemiluminescence in the IR and visible spectral reꢀ
gions. Singlet oxygen is the light emitter in the IR range.
It was found by the IRꢀCL method that the decomposiꢀ
13. A. Gordon and R. A. Ford, The Chemist’s Companion, Wiley,
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Received September 14, 2006;
in revised form December 6, 2006