3-pyrenylacrylates: Synthetic, photophysical, theoretical and electrochemical investigations

Article abstract of DOI:10.5560/ZNB.2013-3004

The Mizoroki-Heck coupling of 1-bromopyrene with acrylates provides a convenient access to a variety of 3-pyrenylacrylates in very good yields (up to 93%). Their photophysical properties combined with solvatochromic effects were studied. In addition, electrochemical oxidation potentials were determined by DPV (differential pulse voltammetry) measurements. The fine structure of the absorbance spectra obtained from photophysical measurements are compared with the results of theoretical calculations performed by time dependent TD-B3LYP methods using the 6-31G* basis set.

Full text of DOI:10.5560/ZNB.2013-3004

3
-Pyrenylacrylates: Synthetic, Photophysical, Theoretical and
Electrochemical Investigations
a,b,e
a,b,c,e
d
a
Sebastian Reimann
, Muhammad Sharif
, Kai Wittler , Leif R. Kn o¨ pke ,
a
d
a,d
a,b
Annette-E. Surkus , Christian Roth , Ralf Ludwig , and Peter Langer
a
Leibniz-Institut f u¨ r Katalyse e.V. an der Universit a¨ t Rostock, Albert-Einstein-Str. 29a, 18059
Rostock, Germany
b
c
d
e
Institut f u¨ r Chemie, Abteilung Organische Chemie, Universit a¨ t Rostock, Albert-Einstein-Str.
3
a, 18059 Rostock, Germany
Department of Chemistry, COMSATS Institute of Information Technology, Abbottabad,
Pakistan
Institut f u¨ r Chemie, Abteilung Physikalische Chemie, Universit a¨ t Rostock, Dr. Lorenz Weg 1,
1
8059 Rostock, Germany
Equal contribution of these co-authors
Reprint requests to P. Langer. Fax: +49-381-498-6410. E-mail: peter.langer@uni-rostock.de
Z. Naturforsch. 2013, 68b, 367 – 377 / DOI: 10.5560/ZNB.2013-3004
Received January 5, 2013
The Mizoroki-Heck coupling of 1-bromopyrene with acrylates provides a convenient access to
a variety of 3-pyrenylacrylates in very good yields (up to 93%). Their photophysical properties com-
bined with solvatochromic effects were studied. In addition, electrochemical oxidation potentials
were determined by DPV (differential pulse voltammetry) measurements. The fine structure of the
absorbance spectra obtained from photophysical measurements are compared with the results of the-
oretical calculations performed by time dependent TD-B3LYP methods using the 6-31G* basis set.
Key words: Arenes, Polycycles, Pyrene, Density Functional Calculations, Electrochemistry, UV/Vis
Spectroscopy
Introduction
by Knoevenagel condensation (Doebner modification)
starting from 1-pyrene carboxaldehyde. They were
Pyrene is a thoroughly investigated and impor- used as probes to monitor polymerization and sur-
tant organic chromophore. Its photophysical proper- face properties by spectroscopic methods [20]. PAA
ties [1 – 5] and its supramolecular chemistry [4 – 9] was applied as an excellent label for tagging poly-
have been widely studied. Structural modifica- electrolytes with a fluorescence probe by copolymer-
tions [10] allow for many applications, which in- ization [21]. The synthesis and photophysical proper-
clude the development of fluorescent dyes [11], molec- ties of 1-ethynylpyrenes and 1-arylpyrenes have been
ular electronics [2, 12], optical sensors [13], field- previously studied as well. They were prepared by
effect transistors [13] and photovoltaic cells [14, 15]. Sonogashira and Suzuki-Miyaura cross-coupling reac-
A wide range of fabrication techniques in combina- tions of halogenated pyrenes and characterized with re-
tion with modern synthetic methods allow for the de- gard to their absorption and emission spectral proper-
velopment of new materials which meet special de- ties [2, 3, 22]. In this respect, the fluorescence prop-
mands and applications. Vinylated pyrene derivatives erties of the parent pyrenes are well known to be
are monomers for the synthesis of specific polymers characterized by long excited-state lifetimes and dis-
containing a pyrene fluorophore attached to the poly- tinct solvatochromic shifts. For example, Marder et al.
mer backbone [16 – 19]. Pyrene acrylic acid (PAA) recently reported the unique range of photophysical
and its methyl ester have been synthesized previously and structural properties of 2- and 2,7-pyrene deriva-
©
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68
S. Reiman et al. · 3-Pyrenylacrylates
Table 1. Synthesis of 3a–j.
O
O
Br
OR
OR
PCy2
iPr
2a−j
2, 3
R
Yield of 3 (%)a
iPr
i
a
b
c
d
e
f
g
h
i
Me
Et
nBu
iBu
tBu
90
87
84
86
93
80
79
88
83
74
iPr
1
3a−j
XPhos
Scheme 1. Synthesis of 3a–j. Conditions: (i) 1 (1.0 equiv.),
a–j (1.2 equiv.), K CO (2.0 equiv.), Pd(OAc) (5 mol-%),
XPhos (10 mol-%), DMF, 60 C, 6 h.
nHex
iOct
2-ethylhexyl
(CH2)2CF3
(CH2)2OH
2
2
3
2
◦
j
tives which differ from those of the more traditional
-substituted pyrene derivatives by high fluorescence
quantum yields and long fluorescence lifetimes [23].
a
Yields of isolated products.
1
◦
Recently, we have reported the synthesis of 1- at 60 C for 6 hours. It was observed that the yields
arylalkenyl)pyrenes by application of the Mizoroki- significantly decreased when the temperature or reac-
(
Heck coupling reaction. Selected alkenylpyrenes, con- tion time was increased. The structures of all products
taining electron donor or electron acceptor sub- were confirmed by spectroscopic techniques (NMR, IR
stituents, were studied regarding their absorption, spectroscopy, mass spectrometry).
emission, and electrochemical properties. The fine
structure of the absorption spectra was compared Photophysical properties
with the electronic states derived from theoretical
calculations [24]. As an extension of our previous Absorption
work [24] we herein report the synthesis of a set of
3
-pyrenylacrylates and their photophysical and sol-
We focussed our work on one representative deriva-
vatochromic properties (Scheme 1) [25]. In addition, tive, e. g. (E)-iso-butyl 3-(pyren-3-yl)acrylate. The
DPV measurements were carried out to determine the electronic absorption spectrum of 3d shows character-
potential values. For a better understanding of the elec- istic patterns which are similar to those in the absorp-
tronic situation of the molecules, calculations were car- tion spectrum of the parent pyrene (Fig. 1) [25, 26].
ried out using the B3LYP TD-DFT method with a 6- In earlier studies it was pointed out that the shape
3
1G* basis set. We studied in detail the physical prop- of electronic absorption spectra of these classes of
erties of one derivative, e. g. (E)-iso-butyl 3-(pyren-3- compounds depends strongly on the pyrene-type back-
yl)acrylate. Since no dramatic changes within the se- bone [2, 24]. While the bands in the spectrum of
1
1
ries of different esters in their general properties were parent pyrene occur at Ba: 241 nm, B : 273 nm,
b
1
1
observed, we compared the data of this example with and La: 335 nm [26], the La band in the spec-
those of a series of 1-(arylalkenyl)pyrenes which were tra of pyrenylacrylate appear at higher wavelengths.
recently prepared by us [24].
Results and Discussion
Synthesis
This can be explained by the extension of the conju-
gated π electron system. The spectrum of 3d, shown
in Fig. 1 contains four bands which have their max-
ima at 199, 234, 277 and 348 nm. Considering that
the electronic structure is similar to that of pyrene,
the latter three bands can be assigned using Platt’s
1
1
The Mizoroki-Heck reaction of 1-bromopyrene nomenclature as Ba transition (234 nm), B transi-
b
1
1
with acrylates 2a–j (1.2 equiv.) afforded the tion (277 nm) and La transition (348 nm). All bands
1
3
-pyrenylacrylates in good to very good yields except the band of the La transition occur at sim-
(
Scheme 1, Table 1). The reaction conditions were ilar wavelengths like the bands in the spectra of
1
1
thoroughly optimized. The best yields were obtained the 1-(arylalkenyl)pyrenes ( Ba: 233 – 238 nm, B :
when the reaction was carried out using Pd(OAc)2 278 – 289 nm, La: 372 – 374 nm) [13]. Furthermore
(
(
b
1
1
5 mol-%), the biarylmonophosphane ligand XPhos the band of the L transition is absent under the se-
b
10 mol-%) and with the reaction carried out in DMF lected analysis conditions.
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S. Reiman et al. · 3-Pyrenylacrylates
369
Fig. 2. Normalized emission spectrum of 3d measured in se-
−
6
−1
lected solvents (c = 1 × 10 mol L ); solvatochromic shift
nd
marked on 2 transition.
Fig. 1. Electronic absorption spectrum of 3d measured in n-
hexane (c = 1 × 10− mol L ).
6
−1
spectra show a more distinct fine structure. This might
be an effect of the formation of intermolecular hydro-
All bands in the spectrum of Fig. 1 show a dis- gen bonds between solvent and substrate [27] or of in-
tinct fine structure which can be ascribed to vibronic tramolecular charge transfer between the pyrene-type
bands. Planar molecules like trans-stilbene and pyrene base which depends on the dipole moment of the sub-
show such vibronic bands in their electronic absorp- strate [2]. Both effects should be favored when the sub-
tion spectra as well, while the spectrum of the less stituent is a polar group like the ester group in case
planar cis-stilbene does not show such bands [3, 26]. of 3d. However, the observed bands in the emission
The vibronic bands in the spectrum of 3d are more dis- spectrum of 3d in n-hexane occur at similar positions
tinct than in the spectra of 1-(arylalkenyl)pyrenes [24]. as the corresponding bands in the spectra of the 1-
Hence, it is likely that 3d has a more planar structure (arylalkenyl)pyrenes which appear at 418 ± 1 nm and
in liquid phase than 1-(arylalkenyl)pyrenes.
442 ± 1 nm, respectively.
Finally solvatochromic studies in selected solvents
have been performed for the elucidation of intermolec-
ular dipole-dipole interactions that affect the emission
Emission
For further photochemical charactization, the emis- spectra. Fig. 2 shows how the maximum of the band in
sion spectrum of 3d has been measured in selected the spectrum of 3d is shifted to higher wavelengths due
solvents (Fig. 2). The spectrum of 3d measured in n- to change of the solvent. The lowest value is observed
hexane shows one broad band with a maximum at in n-hexane with 434 nm while the highest value with
4
34 nm and a shoulder at 418 nm. The asymmetric 454 nm occurs in DMSO. The fine structure of the
shape of the band indicates that there are more tran- band disappears as the maximum is shifted to higher
sitions above 450 nm. However, the bands are super- wavelengths.
posed by each other which prevents making proper
Surprisingly the band shape in the spectrum of 3d
assignments. In general the emission spectrum shows measured in n-hexane is different from the band shapes
fewer details than the spectra of ethynylpyrenes [2] of the spectra of 3d measured in ethyl acetate, diox-
or 1-(arylalkenyl)pyrenes [24]. The absorption spec- ane and THF. In n-hexane a distinct shoulder appears
trum contains a distinct fine structure but the emis- at 418 nm and the maximum of the band occurs at
sion spectrum in n-hexane has less fine structure as 434 nm. The shoulder and the maximum are shifted to
in case of 3d. In contrast, when the absorption spec- longer wavelengths when the solvent is changed. Inter-
trum shows a less pronounced fine structure, like in estingly the shoulder becomes more intense in ethyl ac-
case of the 1-(arylalkenyl)pyrenes [24], the emission etate, dioxane and THF while the intensity of the max-
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70
S. Reiman et al. · 3-Pyrenylacrylates
imum decreases simultaneously. As a result in these
solvents the position of maximum and shoulder are
interchanged so that the band maximum appears at
shorter wavelengths than the respective shoulder. Due
to the loss of fine structure there are no shoulders to
be observed in dichloromethane, DMF, acetonitrile or
DMSO.
The analysis of the spectra shows that the solvent-
substrate interactions are complex. Solvent-substrate
interactions are mainly described as dipole-dipole in-
teractions [28], a more exact description based on non-
empirical constants is difficult [29]. A proper predic-
tion of solvent effects is neither possible based on
terms of simple physical solvent characteristics, nor on
theoretical expressions which could be used for cal-
culations. Hence, most solvent effects are described
on the basis of empirical parameters of solvent polar-
Fig. 3. Oxidative DPVs of 3d and the precursors, pyrene
−1
and 1-bromopyrene in DMF (0.1 mol L TBABF ); work-
4
ing electrode: platinum. Inset depicts oxidative DPVs of
ity. The importance of the parameters introduced by formerly investigated 1-(arylalkenyl)pyrenes [24] under the
Kamlet and Taft [28] to explain solvatochromic shifts
has been demonstrated successfully in case of ethynyl-
same conditions.
and 1-(arylalkenyl)pyrenes [2, 24]. In both studies, the values of 3d in comparison to the precursors pyrene
∗
influencing factor was the polarity/polarizability π . and 1-bromopyrene. The oxidative DPV of 3d exhibits
The shift to longer wavelength increases with increas- three oxidation peaks. Two of them can also be found
∗
ing value of π . Referring to Fig. 2 the solvatochromic in the DPVs of the precursors (cf. Fig. 3).
∗
shift in the spectra of 3d can also be assigned to π .
The oxidative peaks of pyrene are located at 1.42
∗
The value of π is −0.08 in n-hexane and +1.00 in and 1.58 V. In case of 1-bromopyrene, containing the
DMSO. However, the spectra measured in acetonitrile electron-withdrawing bromine substituent, a shift of
∗
(
π = 0.75) shows a greater solvatochromic shift than these peaks to positive potentials (1.50 and 1.60 V)
the spectra measured in dichloromethane (π = 0.82) can be observed. The second oxidation peak of 1-
or DMF (π = 0.88). Although π is adequate to ex- bromopyrene is not well developed and can only be
plain the loss of fine structure, there is no explanation detected as a shoulder of the first oxidation peak. The
for the peculiar band shape evolution in solvents like acrylate substituent of 3-pyrenylacrylate 3d does not
ethyl acetate, dioxane or THF. For these solvents the seems to have a strong electron withdrawing effect and,
∗
∗
∗
∗
value of π is about 0.55 which is lower than the values therefore, the oxidative peaks are found at 1.45 and
for the previously mentioned solvents, but still higher 1.62 V (only weakly developed). The third oxidation
as compared to n-hexane. The analyses of the remain- peak at 1.33 V results from the influence of the acrylate
ing solvent parameters of Kamlet, of Taft’s α and β group. A comparison with the formerly investigated 1-
(see Supporting Information for definition and for se- (arylalkenyl)pyrenes [24] (Fig. 3) reveals that the best-
lected values of α and β; see note at the end of the pa- developed oxidative peak between 1.0 and 1.2 V can
per for availability) or of other constants like the dipole not be found for 3-pyrenylacrylate 3d. This peak is as-
moment or the dielectric constant, all do not allow for signed to the oxidation of the aryl system.
a sufficient explanation of the observed peculiar band
shape evolution
Computational studies
Electrochemical studies
Exploring the geometric and electronic structure of
the molecules, we carried out density functional the-
Cyclovoltammetric and DPV (Differential Pulse ory (DFT) calculations, using Becke’s three parameter
Voltammetry) measurements were carried out to de- set with Lee-Yang-Parr modification (B3LYP) and the
termine the electrochemical activity and the potential 6-31G* basis set for geometry optimization [30 – 32].
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S. Reiman et al. · 3-Pyrenylacrylates
371
Fig. 5 (color online). Calculated electronic spectrum (black
solid line) as sum of single Gaussian functions (short dashed
1
1
1
lines, colored according to the bands La, B , Ba and II)
b
and the experimental absorbance spectra (solid grey lines)
for the product 3d. The right axis corresponds to the exper-
imental absorbance spectrum. Inlay: Calculated spectrum of
Fig. 4 (color online). Structure, electrostatic potential sur-
face, HOMO and LUMO molecular orbitals and the dipole
moment of compound 3d.
1-(arylalkenyl)pyrenes from our previous work [24] for com-
parison.
Furthermore, for the calculation of the excitation en- Table 2. Excited states, excitation energies and oscillator
1
ergies we used the TD-DFT method with the B3LYP strengths f ≥ 0.04, 8% percentage of the strongest band La,
which are mainly responsible for the distinct maxima in the
functional. The 6-31G* basis set is basically small, but
absorption spectra of the 3-pyrenylacrylate.
it yields a better fit of excitation energies to the ex-
perimental data than higher basis sets. The latter ones Band
State
λ (nm)
f
1
La
1
6
8
391.43
285.49
266.10
230.97
228.91
225.70
223.26
220.89
216.85
205.00
203.42
200.68
196.29
190.16
0.519
0.328
0.187
0.045
0.123
0.037
0.465
0.049
0.055
0.037
0.116
0.077
0.085
0.228
result in a stronger red shift of the bands in the ab-
sorbance spectra.
The geometry optimization reveals – as shown in
Fig. 4 – that product 3d is not planar: The pyrene
groups is, due to steric effects, twisted against the
ethylene group which was also observed for 1-
1
Bb
1Ba
12
13
14
1
1
1
5
6
7
(arylalkenyl)pyrenes in our previous study [24]. As the
calculations refer to the gas phase, the structures in so-
lution might be different.
II
22
23
2
2
2
4
7
8
The dipole moment of 2.5 D is relatively high and is
the reason for strong intermolecular interactions in so-
lution. We have shown in our previous study [24] that
the fine structure in the emission spectra is sensitive to
∗
the polarity/polarizability π of the solvent. In solvents
The excitation energies and the corresponding os-
∗
with low values of π , intermolecular dipole-dipole in- cillator strengths were determined by using the TD-
teractions provoke the loss of fine structure in the spec- B3LYP method (Table 2, Fig. 5). The resulting spec-
tra. However, in the present study, none of the emission trum and its decomposition were calculated as it is de-
spectra, recorded in different solvents, possess a fine scribed in our previous work [24]. TD-DFT excitation
structure. Obviously, the strong dipole moment of 3d energies are typically slightly redshifted with respect to
causes strong substrate/solvent interactions and, there- the experimental data [33]. The lowest excitation state,
1
fore, a loss of the fine structure in the emission spec- which is assigned to band La (according to the nota-
∗
trum is independent from the polarity/polarizability π
of the solvent.
tion in Fig. 1) appears at about 391 nm. One signifi-
cant contribution (cf. red dashed lines in Fig. 5) of this
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72
S. Reiman et al. · 3-Pyrenylacrylates
∗
band can be assigned to the HOMO-LUMO or π-π
missing fine structure in all spectra of 3d recorded in
selected solvents. The observed solvatochromic shifts
transition.
1
1
In contrast the wavelength of the bands La, B , are similar to those observed for other classes of sub-
b
1
Ba and II of the 1-(arylalkenyl)pyrenes are blue- stituted pyrenes.
shifted by about 10 – 20 nm [24]. Hence, the spa-
tial distribution of the delocalized π systems of the
Experimental Section
3
-pyrenylacrylates, which contain no phenyl group,
General comments
is smaller than that of the π systems of the 1-
(
arylalkenyl)pyrenes and affects the excitation ener-
All reactions were carried out in oven-dried pressure
tubes under argon atmosphere. Pyrene, palladium(II) acetate,
the 2-dicyclohexylphosphanyl-2 ,4 ,6 -tri-isopropyl biphenyl
ligand (XPhos) and the corresponding acrylates were pur-
nd
gies significantly. Furthermore, the NBO [34 – 40] 2
order perturbation calculation shows that the interac-
tion energy between the bonding orbitals of the ethy-
0
0
0
lene group and the antibonding orbitals of the car- chased from a Aldrich. Dry solvents (DMF, DCM) were
−1
bonyl group is about 21 kcal mol while the strongest purged with argon before use. K CO was purchased from
2
3
interaction energy between this ethylene group and Aldrich, dried and mortared before use. Thin layer chro-
−
1
the pyrenyl group is about 9 kcal mol . Therefore, matography (TLC) was run on Merck precoated aluminum
plates (Si 60 F254). Column chromatography was performed
the electron withdrawing carboxy group hinders the
using Merck Silicagel 60 (0.043 – 0.06 mm). NMR data were
formation of a delocalized π system over the entire
recorded on Bruker ARX 300 and ARX 400 spectrome-
molecule. Thus, the ethylene group interacts predomi-
1
3
1
ters. C and H NMR spectra were referenced to signals
of deuterated solvents and residual protonated solvents, re-
spectively. Gas chromatography-mass analysis was carried
out on an Agilent HP-5890 instrument with an Agilent HP-
nantly with the carboxy group forming a planar unit.
Conclusion
5
973 Mass Selective Detector (EI) and an HP-5 capillary
In conclusion, 3-pyrenylacrylates were prepared by
Heck reaction of 1-bromopyrene with acrylates in good
to very good yield. DPV measurements were used to
column using helium as carrier gas. ESI HR-MS measure-
ments were performed on an Agilent 1969A TOF mass spec-
trometer. All UV/Vis spectra were recorded on a Lambda
study their electrochemical behavior. Similar to our 5 (Perkin Elmer) spectrophotometer with a concentration of
−6
−1
former results with 1-(arylalkenyl)pyrenes [24] the ox- c = 10 mol L . All fluorescence spectra were recorded on
idation potentials exhibit a dependence on the nature a Hitachi F-4010 fluorescence spectrophotometer using sim-
of the substituent. The photochemical investigations ilar solution concentrations in various solvents.
have shown that the selected 3-pyrenylacrylate 3d has
similar properties as the 1-(arylalkenyl)pyrenes of our
DPV studies
last study [24]. Comparing the absorption spectrum of
d with the spectra of other pyrenyl derivatives like under argon atmosphere in the presence of tetrabutylammo-
Studies were performed at room temperature in dry DMF
3
−
1
ethynylpyrenes [2] or 1-(arylalkenyl)pyrenes [24] it nium tetrafluoroborate (0.1 mol L ) as conducting salt us-
has turned out that the band of the La transition is sen- ing an Autolab (PGSTAT 302N, Eco Chemie). The work-
1
ing electrode was a platinum disk electrode (Eco Chemie,
sitive to the size of the conjugated π electron system
d = 2 mm), the counter electrode a laboratory-made Pt plate
electrode. Via 3 M KCl salt bridge the reference electrode
Ag/AgCl/3 M KCl (Sensortechnik Meinsberg GmbH) was
connected. All potentials mentioned in this paper were mea-
sured with regard to this reference system and were checked
by using the ferrocene/ferrocenium internal reference sys-
tem. The CV scans were done three times at a scan rate of
5 mV s . The differential pulse voltammograms were per-
formed in oxidative and in reductive direction with a scan
which is introduced by substituting the pyrene moi-
ety. By contrast the bands of the other transitions like
1
1
Ba and B , are less affected by the size of the con-
b
jugated π electron system. The TD-DFT calculations
and the NBO analysis have confirmed that – compared
to the 1-(arylalkenyl)pyrenes – the conjugated π elec-
tron system of the title compounds is smaller and more
separated. The shape of the fine structure occurring in
the absorption and emission spectra seems to be also
strongly dependent on the class of the substituent. The
−1
2
−1
rate of 5 mV s
(step potential 2.5 mV, modulation am-
plitude 25 mV, modulation time 0.05 s, interval time 0.5 s).
−1
DFT calculation gave a high dipole moment of 2.5 D Concentrations of 1 mmol L analyt were used for the mea-
of the molecule, which seems to be the reason for the surements.
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S. Reiman et al. · 3-Pyrenylacrylates
373
Theoretical calculations
centrated in vacuo. The residue was purified by column chro-
matography (n-hexane-ethyl acetate) to afford 3.
The optimization of the structures and electrostatic po-
tential surface were calculated with the 6-31G* basis sets (E)-Methyl 3-(pyren-3-yl)acrylate (3a)
and the Becke3LYP density functional method [31, 32] by
Starting with 1 (100 mg, 0.35 mmol), 2a (46.0 mg,
.53 mmol), Pd(OAc)2 (5 mol-%, 4.3 mg, 0.017 mmol),
XPhos ligand (10 mol-%, 16.0 mg, 0.035 mmol), K CO
using the GAUSSIAN 09 package [30]. For the B3LYP
method the Becke-3 parameter gradientcorrected exchange
functional is combined with the gradient-corrected corre-
lation LYP functional by Lee, Yang and Parr. No imag-
inary frequencies were found indicating that all geome-
tries represent at least local minimum structures on the
potential energy surface. The calculation of the 30 elec-
tron transition states requires the solution of the time-
dependent Schr o¨ dinger equations and was carried out by
using the time-dependent density functional theory (TD-
DFT) method with the B3LYP functional. Orbitals and ener-
gies, atomic charges, vibrational modes and thermodynamic
properties were chosen as output parameters. HOMO and
LUMO orbital surfaces and electrostatic potential density
maps were then obtained from the output. Additionally we
calculated the natural atomic charges by applying the NBO
program [41, 42] as implemented in GAUSSIAN 09 [30]. All
calculations have been carried out on the HPPC cluster in
Rostock.
0
2
3
(
98.0 mg, 0.71 mmol) in DMF (5 mL), 3a was isolated as
◦
1
a yellow solid (91 mg, 90%); m. p. 135 – 137 C. – H NMR
(
1
300 MHz, CDCl ): δ = 3.82 (s, 3H, OCH ), 6.62 (d, J =
3
3
5.6 Hz, 1H, CH), 7.92 – 8.19 (m, 8H, CH), 8.39 (d, J =
.3 Hz, 1H, CH), 8.75 (d, J = 15.9 Hz, 1H, CH) ppm. –
C NMR (75 MHz, CDCl ): δ = 51.9 (OCH ), 119.8 (CH),
9
1
3
3
3
1
1
1
1
22.5 (CH), 124.2 (CH), 124.7 (C), 124.9 (C), 125.1 (CH),
25.9 (CH), 126.0 (CH), 126.3 (CH), 127.4 (CH), 128.2 (C),
28.6 (CH), 128.9 (CH), 129.8 (C), 130.7 (C), 131.3 (C),
−
1
32.8 (C), 141.6 (CH), 167.6 (CO) ppm. – IR (ATR, cm ):
ν˜ = 3072 (w), 3043 (w), 2956 (w), 2927 (w), 2859 (w), 1700
(
(
–
2
1
s), 1611 (m), 1592 (w), 1433 (m), 1368 (m), 1273 (m), 1121
m), 1071 (m), 982 (m), 838 (s), 760 (m), 707 (m), 677 (w).
+
GC-MS (EI, 70 eV): m/z (%) = 286 (58) [M] , 255 (14),
28 (18), 227 (100), 226 (93), 225 (15), 224 (18), 200 (8),
13 (26), 112 (12). – HRMS ((+)-EI): m/z = 286.098350
+
(
calcd. 286.09883 for C H O [M] ).
2
0 14 2
Synthesis of 1-bromopyrene (1)
(E)-Ethyl 3-(pyren-1-yl)acrylate (3b)
The synthesis of 1-bromopyrene was carried out af-
ter a known literature procedure [43] To a stirred solu-
tion of pyrene (2.02 g, 10.0 mmol) and hydrobromic acid
Starting with 1 (100.0 mg, 0.355 mmol), 2b (53.2 mg,
.532 mmol), Pd(OAc)2 (5 mol-%, 4.3 mg, 0.017 mmol),
0
XPhos ligand (10 mol-%, 16.0 mg, 0.035 mmol), K CO
2
3
(1.24 mL, 48%, 11.0 mmol) in methanol-ether (20 mL, 1 : 1)
(
98.0 mg, 0.71 mmol) in DMF (5 mL), 3b was isolated as
was slowly added hydrogen peroxide (0.34 g; 0.86 mL of
◦
1
a yellow solid (92 mg, 87%); m. p. 94 – 96 C. – H NMR
a 35% aqueous solution; 10 mmol) over a period of 15 min
(
(
7
(
300 MHz, CDCl ): δ = 1.34 (t, J = 6.98 Hz, 3H, CH ), 4.29
3 3
◦
at 10 – 15 C. The reaction was left at room temperature for
q, J = 14.3 Hz, 2H, CH ), 6.26 (d, J = 15.74 Hz, 1H, CH),
2
1
4 h while its progress was monitored by TLC. After the
.92 – 8.12 (m, 8H, Py), 8.34 (d, J = 9.23 Hz, 1H, Py), 8.75
completion of monobromination, the solvent was removed
under reduced pressure and the crude product was taken up
in ethyl acetate and washed with water and brine and dried
over anhydrous sodium sulfate. The pure product was iso-
lated by column chromatography on silica gel to get pure
13
d, J = 15.74 Hz, 1H, CH) ppm. – C NMR (62.89 MHz,
CDCl ): δ = 30.9 (CH ), 61.2 (0CH ), 120.3 (CH), 122.5
3
3
2
(
(
(
(
CH), 122.9 (C), 124.1 (CH), 124.6 (C), 124.8 (CH), 125.0
CH), 125.7 (CH), 125.8 (C), 125.9 (CH), 126.2 (CH), 127.3
CH), 127.4 (C), 128.3 (C), 128.4 (CH), 128.5 (C), 129.7
C), 130.7 (C), 131.3 (C), 132.6 (C), 141.3 (CH), 167.1 (CO)
1
-bromopyrene as a slightly yellow solid (95%, 2.67 g).
−1
ppm. – IR (ATR, cm ): ν˜ = 3041 (w), 2977 (w), 2925 (w),
General procedure for the synthesis of
2
1
904 (w), 2852 (w), 1731 (w), 1705 (m), 1619 (m), 1538 (w),
479 (w), 1442 (m), 1391 (w), 1340 (w), 1277 (m), 1210 (m),
3
-pyrenylacrylates 3
Palladium(II) acetate (5 mol-%) and XPhos (10 mol-%) 1156 (s), 1107 (m), 1053 (m), 971 (m), 897 (m), 837 (s), 788
were placed under argon atmosphere in a pressure tube (m), 748 (m), 700 (m), 616 (m), 593 (m). – MS (EI, 70 eV):
+
and 5 mL of DMF was added. After stirring for 15 min, 1- m/z (%) = 300(64) [M] , 255 (16), 227 (100), 226 (86), 224
bromopyrene (1), the acrylate 2a–j and K CO were added. (13), 113 (27). – HRMS ((+)-EI): m/z = 300.11448 (calcd.
2
3
◦
+
Subsequently, the mixture was heated at 60 C for 6 h. To the 300.114633 for C21H16O2, [M+H] ).
mixture were added water and CH Cl (20 mL) and the or-
ganic and the aqueous layer were separated. The latter was
2
2
(E)-Butyl 3-(pyren-1-yl)acrylate (3c)
extracted with CH Cl (2 × 20 mL). The combined organic
Starting with 1 (100 mg, 0.35 mmol), 2c (68.0 mg,
layers were dried (Na SO ), filtered and the filtrate was con- 0.53 mmol), Pd(OAc)2 (5 mol-%, 4.3 mg, 0.017 mmol),
2
2
2
4
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S. Reiman et al. · 3-Pyrenylacrylates
XPhos ligand (10 mol-%, 16.0 mg, 0.035 mmol), K CO
(98.0 mg, 0.71 mmol) in DMF (5 mL), 3e was isolated as
2
3
1
(
98 mg, 0.71 mmol) in DMF (5 mL), 3c was isolated as a luminous yellow oil (108 g, 93%). – H NMR (300 MHz,
1
a luminous yellow oil (98 mg, 84%) – H NMR (300 MHz, CDCl ): δ = 0.97 (s, 9H, CH ), 6.55 (d, J = 15.9 Hz, 1H,
3
3
CDCl ): δ = 1.01 (t, J = 7.4 Hz, 3H, CH ), 1.50 (m, 2H, CH), 7.96 (d, J = 15.6 Hz, 1H, CH), 7.97 – 8.18 (m, 7H, CH),
3
3
CH ), 1.77 (d, J = 6.8 Hz, 2H, CH ), 4.31 (t, J = 6.7 Hz, 8.37 (d, J = 9.0 Hz, 1H, CH), 8.69 (d, J = 15.8 Hz, 1H, CH)
2
2
1
3
2
4
H, OCH ), 7.83 (d, J = 7.84 Hz, 3H, CH), 7.89 – 8.00 (m, ppm. – C NMR (75 MHz, CDCl ): δ = 28.4 (CH , tBu),
2 3 3
H, Py), 8.03 – 8.12 (m, 4H, Py), 8.13 – 8.23 (m, 2H, Ar) 80.7 (C, tBu), 122.3 (CH), 124.2 (CH), 124.8 (C), 124.9
1
3
ppm. – C NMR (62.89 MHz, CDCl ): δ = 13.2 (CH ), (C), 125.0 (CH), 125.7 (CH), 125.9 (CH), 126.3 (CH), 127.4
2
3
3
7.6 (CH ), 35.1 (CH ), 59.6 (OCH ), 121.9 (CH), 123.8 (CH), 128.4 (C), 128.5 (CH), 128.8 (CH), 128.9 (CH), 129.6,
2 2 2
(
1
1
CH), 123.9 (2CH), 124.8 (CH), 125.8 (CH), 126.0 (CH), 130.8, 131.4, 132.5 (C), 140.3 (CH), 166.5 (CO) ppm. – IR
−
1
26.4 (CH), 126.5 (CH), 127.5 (C), 127.7 (CH), 129.1 (C), (ATR, cm ): ν˜ = 3042 (w), 2959 (w), 2928 (w), 2859 (w),
29.8 (CH), 130.3 (C), 133.5 (C), 135.9 (C), 140.3 (C), 171.9 1705 (m), 1621 (m), 1596 (m), 1458 (w), 1390 (w), 1276 (s),
−
1
(
(
(
(
(
5
CO) ppm. – IR (ATR, cm ): ν˜ = 3433 (w), 3039 (w), 2955 1143 (s), 1070 (m), 1039 (w), 976 (m), 840 (s), 743 (w), 706
+
w), 2869 (w), 2135 (w), 1920 (w), 1796 (w), 1720 (s), 1619 (m), 680 (w). – GC-MS (EI, 70 eV): m/z (%) = 328 [M] ,
m), 1594 (m), 1537 (w), 1487 (w), 1434 (w), 1381 (w), 1312 (44), 255 (26), 248 (30), 228 (19), 227 (100), 226 (88), 225
m), 1274 (m), 1200 (m), 1162 (s), 1061 (m), 973 (m), 900 (17), 224 (22). – HRMS ((+)-EI): m/z = 328.145734 (calcd.
w), 838 (s), 795 (m), 731 (m), 680 (m), 635 (m), 594 (m), 328.14578 for C H O [M] ).
+
2
3 20 2
+
38 (m). – MS (EI, 70 eV): m/z (%) = 328 (61) [M] , 255
(19), 227 (100), 226 (85), 225 (12), 224 (12), 113 (18). – (E)-Hexyl 3-(pyren-1-yl)acrylate (3f)
HRMS ((+)-EI): m/z = 328.145349 (calcd. 328.14578 for
+
C H O [M+H] ).
2
3
20
2
Starting with 1 (100 mg, 0.35 mmol), 2f (82.9 mg,
.53 mmol), Pd(OAc)2 (5 mol-%, 4.3 mg, 0.017 mmol),
0
(
E)-iso-Butyl 3-(pyren-3-yl)acrylate (3d)
Xphos ligand (10 mol-%, 16.0 mg, 0.035 mmol), K CO
2
3
(
98 mg, 0.71 mmol) in DMF (5 mL), 3f was isolated as a yel-
Starting with 1 (100 mg, 0.35 mmol), 2d (76.0 mg,
.53 mmol), Pd(OAc)2 (5 mol-%, 4.3 mg, 0.017 mmol),
1
low oil (101 mg, 80%). – H NMR (300 MHz, CDCl3):
δ = 0.86 (t, J = 7.1 Hz 3H, CH ), 1.26 – 1.41 (m, 6H, CH ),
1
6
0
3
2
XPhos ligand (10 mol-%, 16.0 mg, 0.035 mmol), K CO
2
3
.70 (d, J = 6.7 Hz 2H, CH ), 4.22 (t, J = 6.76, 2H, OCH2),
2
(
98.0 mg, 0.71 mmol) in DMF (5 mL), 3d was isolated as
.62 (d, J = 15.73, 1H, CH), 7.90 – 8.19 (m, 8H, Py), 8.38
1
a luminous yellow oil (100 mg, 86%). – H NMR (300 MHz,
3
(d, J = 9.41 Hz, 1H, CH), 8.73 (d, J = 15.73 Hz, 1H, CH)
CDCl ): δ = 0.97 (d, J = 6.6 Hz, 6H, CH ), 2.05 – 1.99
3
3
13
ppm. – C NMR (75 MHz, CDCl ): δ = 14.1 (CH ), 22.6
3
3
(
1
(
1
1
1
1
(
1
m, 1H, CH), 4.00 (d, J = 6.6 Hz, 2H, CH ), 6.61 (d, J =
2
(CH ), 25.8 (CH ), 28.8 (CH ), 31.6 (CH ), 64.9 (OCH ),
2 2 2 2 2
5.6 Hz, 1H, CH), 7.89 (d, J = 15.5 Hz, 1H, CH), 7.91 – 8.15
1
1
1
1
20.4 (CH), 122.5 (CH), 124.2 (CH), 124.6 (C), 124.9 (CH),
25.0 (CH), 125.8 (CH), 126.0 (CH), 126.3 (CH), 127.2 (C),
27.3 (CH), 128.3 (C), 128.5 (CH), 129.7 (C), 130.7 (C),
31.3 (C), 132.7,(C), 141.3 (CH), 167.3 (CO) ppm. – IR
m, 7H, CH), 8.31 (d, J = 8.4 Hz, 1H, CH), 8.70 (d, J =
5.8 Hz, 1H, CH) ppm. – 13C NMR (75 MHz, CDCl ): δ =
3
9.3 (CH ), 19.3 (CH ), 28.0 (CH), 70.9 (CH ), 120.3 (CH),
3
3
2
22.4 (CH), 124.2 (CH), 124.6 (C), 124.9 (C), 125.0 (CH),
25.8 (CH), 125.9 (CH), 126.3 (CH), 127.3 (CH), 128.3
−1
(
1
ATR, cm ): ν˜ = 3040 (w), 2952 (m), 2926 (m), 2855 (w),
918 (w), 1707 (s), 1620 (m), 1478 (w), 1416 (w), 1368
C), 128.5 (CH), 128.6 (CH), 129.7, 130.7, 131.3, 132.7 (C),
(
(
(
w), 1313 (m), 1241 (m), 1162 (s), 1053 (m), 975 (m), 840
s), 794 (w), 716 (w), 680 (w), 609 (w), 536 (w). – GC-MS
EI, 70 eV): m/z (%) = 356 (44) [M] , 167 (36), 149 (100),
−1
41.3 (CH), 167.3 (CO) ppm. – IR (ATR, cm ): ν˜ = 3040
(
w), 2958 (w), 2872 (w), 1703 (m), 1619 (m), 1595 (m),
+
1
8
7
2
466 (w), 1374 (w), 1240 (m), 1153 (s), 1013 (m), 971 (m),
39 (s), 755 (m), 704 (m), 679 (w), 488 (w). – GC-MS (EI,
2
28 (19), 227 (100). – HRMS ((+)-EI): m/z = 356.176071
+
(calcd. 356.17708 for C H O [M] ).
+
25 24 2
0 eV): m/z (%) = 328 [M] , 255 (31), 249 (30), 228 (23),
27 (100), 226 (96), 225 (12), 224 (16), 113 (15). – Anal.
(E)-6-Methylheptyl 3-(pyrene-1-yl)acrylate (3g)
for C23 H O (328.40): calcd. C 84.12 H 6.14; found C
20
2
8
3
3.97 H 6.241. – HRMS ((+)-EI): m/z = 328.145716 (calcd.
+
Starting with
1 (100 mg, 0.35 mmol), 2g (98 mg,
28.14578 for C H O [M] ).
2
3 20 2
0
.53 mmol), Pd(OAc)2 (5 mol-%, 4.3 mg, 0.017 mmol),
Xphos ligand (10 mol-%, 16.0 mg, 0.035 mmol), K CO
3
(
E)-tert-Butyl 3-(pyren-3-yl)acrylate (3e)
2
(
98.0 mg, 0.71 mmol) in DMF (5 mL), 3g was isolated
1
Starting with 1 (100 mg, 0.35 mmol), 2 e (76.0 mg, as a yellow oil (107.1 mg, 79%) – H NMR (300 MHz,
.53 mmol), Pd(OAc)2 (5 mol-%, 4.3 mg, 0.017 mmol), CDCl ): δ = 0.76 – 0.90 (m, 8H), 1.19 – 1.37 (m, 7H, CH ),
0
3
2
Xphos ligand (10 mol-%, 16.0 mg, 0.035 mmol), K CO
4.13 – 4.16 (m, 2H, OCH ), 7.91 – 8.22 (m, 9H, Py), 8.39 (d,
2
3
3
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375
J = 9.15 Hz, 1H, CH), 9.75 (d, J = 15.63 Hz, 1H, CH) ppm. 124.7 (C), 125.0 (CH), 125.2 (CH), 126.1 (CH), 126.3 (CH),
1
3
–
2
6
C NMR (75 MHz, CDCl ): δ = 10.1 (CH ), 14.1 (CH ), 126.4 (CH), 127.4 (CH), 128.6 (C), 128.9 (CH), 129.9,
3 3 3
3.0 (CH ), 23.8 (CH ), 28.9 (CH ), 30.4 (CH ), 38.7 (CH), 131.8, 133.5, 133.7 (C), 143.8 (CH), 166.9 (CO) ppm. – IR
8.2 (OCH ), 120.4 (CH), 122.5(CH), 124.2 (CH), 125.1 (ATR, cm ): ν˜ = 3045 (w), 2956 (w), 2922 (w), 2852 (w),
CH), 125.8 (CH), 126.0 (CH), 126.3 (CH), 127.3 (CH), 1718 (m), 1614 (m), 1538 (m), 1441 (w), 1371 (w), 1267 (m),
2
2
2
2
−
1
2
(
1
1
1
28.3 (C), 128.5 (CH), 128.8 (CH), 129.7 (C), 130.7 (C), 1138 (s), 1054 (w), 973 (w), 839 (s), 755 (w), 701 (m), 678
+
30.9 (CH), 131.3 (C), 132.5, (C), 132.7 (C), 141.3 (C), (w). – GC-MS (EI, 70 eV): m/z (%) = 354 (90) [M] , 255
−
1
67.8 (CO) ppm. – IR (ATR, cm ): ν˜ = 3435 (w), 3041 (23), 228 (19), 227 (100), 226 (92), 225 (15), 224 (17), 113
(
(
(
(
w), 2955 (w), 2870 (w), 2731 (m), 1722 (s), 1621 (m), 1584 (34), 112 (13). – HRMS ((+)-EI): m/z = 354.086153 (calcd.
w), 1510 (w), 1460 (m), 1416 (w), 1312 (m), 1270 (s), 1209 354.08622 for C H F O [M] ).
m), 1163 (m), 1120 (m), 1070 (m), 1039 (m), 975 (m), 866
m), 841 (s), 741 (m), 705 (m), 651 (w), 609 (w), 538 (w). (E)-2-Hydroxyethyl 3-(pyren-3-yl)acrylate (3j)
+
2
1 13 3 2
–
HRMS ((+)-EI): m/z = 384.207745 (calcd. 384.20838 for
+
C H O [M] ).
Starting with 1 (100 mg, 0.35 mmol), 2j (56.0 mg,
.53 mmol), Pd(OAc)2 (5 mol-%, 4.3 mg, 0.017 mmol),
2
7 28 2
0
(E)-2-Ethylhexyl 3-(pyren-3-yl)acrylate (3h)
Xphos ligand (10 mol-%, 16.0 mg, 0.035 mmol), K CO
2
3
(
98.0 mg, 0.71 mmol) in DMF (5 mL), 3j was isolated as
Starting with 1 (100 mg, 0.35 mmol), 2h (111 mg,
.53 mmol), Pd(OAc)2 (5 mol-%, 4.3 mg, 0.017 mmol),
◦
1
a yellow solid (84 mg, 74%); m. p. 132 – 134 C. – H NMR
300 MHz, CDCl ): δ = 1.99 (s, 1H, OH), 3.86 – 3.89 (m,
0
(
3
Xphos ligand (10 mol-%, 16.0 mg, 0.03 mmol), K CO
2
3
2
1
1
H, CH ), 4.33 – 4.37 (m, 2H, CH ), 6.63 (d, J = 15.9 Hz,
2
2
(
98 mg, 0.71 mmol) in DMF (5 mL), 3h was isolated as a yel-
H, CH), 7.89 – 8.01 (m, 8H, CH), 8.38 (d, J = 8.6 Hz,
1
low oil (120 mg, 88%). – H NMR (300 MHz, CDCl3):
13
H, CH), 8.74 (d, J = 15.9 Hz, 1H, CH) ppm. – C NMR
δ = 0.81 – 0.90 (m, 6H, CH ), 1.23 – 1.46 (m, 8H, CH ),
3
2
(
(
(
75 MHz, CDCl ): δ = 61.6, 66.4 (CH ), 119.4 (CH), 122.4
CH), 124.2 (CH), 124.3 (CH), 124.6 (C), 124.7 (C), 125.1
CH), 125.9 (CH), 126.1 (CH), 126.3 (CH), 127.3 (CH),
3 2
1
6
8
.65 – 1.71 (m, 1H, CH), 4.15 (d, J = 6.3 Hz, 2H, OCH2),
.66 (d, J = 15.6 Hz, 1H, CH), 7.85 – 8.07 (m, 8H, CH),
.24 (d, J = 8.7 Hz, 1H, CH), 8.75 (d, J = 15.8 Hz, 1H,
1
28.7 (CH), 130.7, 130.9, 131.3, 132.6, 132.9 (C), 142.3
1
3
CH) ppm. – C NMR (75 MHz, CDCl ): δ = 11.2 (CH ),
−1
3
3
(
2
CH), 167.5 (CO) ppm. – IR (ATR, cm ): ν˜ = 3024 (w),
1
6
(
(
1
(
4.2 (CH ), 23.0, 23.8, 29.1, 30.6 (CH ), 39.0 (CH chain),
3
2
961 (w), 2920 (w), 2875 (w), 1698 (m), 1617 (m), 1599
7.2 (OCH ), 120.4 (CH), 122.5 (CH), 124.2 (CH), 124.7
2
(m), 1435 (w), 1361 (w), 1276 (m), 1088 (s), 1036 (w),
C), 124.9 (C), 125.1 (CH), 125.8 (CH), 126.0 (CH), 126.3
CH), 127.4 (CH), 128.3 (C), 128.6 (CH), 128.6 (CH), 129.7,
9
7
79 (w), 838 (s), 760 (w), 703 (m), 678 (w). – GC-MS (EI,
+
0 eV): m/z (%) = 316 (63) [M] , 255 (28), 248 (30), 228
30.7, 131.4, 132.7 (C), 141.3 (CH), 167.4 (CO) ppm. – IR
(20), 227 (98), 226 (100), 225 (13), 224 (15), 113 (24). –
−1
ATR, cm ): ν˜ = 3041 (w), 2956 (w), 2925 (w), 2857 (w),
709 (m), 1620 (m), 1595 (m), 1459 (w), 1379 (w), 1275
HRMS ((+)-EI): m/z = 316.108872 (calcd. 316.10940 for
C H O [M] ).
1
(
+
2
16
1 3
m), 1162 (s), 1030 (w), 975 (w), 840 (s), 756 (w), 705
(
[
m), 680 (w). – GC-MS (EI, 70 eV): m/z (%) = 384 (100)
M] , 272 (17), 255 (36), 248 (30), 228 (24), 227 (88), 226
Supporting information
+
(
8
78), 225 (10), 224 (10). – Anal. for C27 H O : calcd. C
28 2
Definition and selected Taft’s α and β values are
4.34, H 7.34; found C 83.89, H 7.652. – HRMS ((+)-EI):
given as Supporting Information available online (DOI:
1
+
m/z = 384.208096 (calcd. 384.20838 for C H O [M] ).
27 28 2
0.5560/ZNB.2013-3004).
(E)-2,2,2-Trifluoroethyl 3-(pyren-3-yl)acrylate (3i)
Acknowledgement
Starting with
1 (100 mg, 0.35 mmol), 2i (67 mg,
0
.532 mmol), Pd(OAc)2 (5 mol-%, 4.3 mg, 0.017 mmol),
We are grateful to the Higher Education Commission
Pakistan (scholarship for M. S.). A. Lehmann (LIKAT) is
Xphos ligand (10 mol-%, 16.0 mg, 0.035 mmol), K CO
2
3
(
98.0 mg, 0.71 mmol) in DMF (5 mL), 3i was isolated as a lu- gratefully acknowledged for measuring the absorption spec-
◦
minous yellow solid (105 mg, 83%); m. p. 118 – 120 C. – tra. Financial support by the University of Rostock (schol-
1
H NMR (300 MHz, CDCl ): δ = 4.75 (q, J = 9.0 Hz, 2H, arship of the Interdisciplinary Faculty of the University of
3
OCH CF ), 6.66 (d, J = 15.0 Hz, 1H, CH), 8.08 – 8.37 (m, Rostock/Dept. LLM for S R and C R) and by the state of
2
3
8
1
H, CH), 8.24 (d, J = 9.0 Hz, 1H, CH), 8.99 (d, J = 15.0 Hz, Mecklenburg-Vorpommern is gratefully acknowledged. Fi-
H, CH) ppm. – 13C NMR (75 MHz, CDCl ): δ = 68.1 nancial support by the European Social Fund (EFRE pro-
3
(OCH ), 117.6 (CH), 122.5 (CH), 124.3 (CH), 124.7 (C), gram) is also acknowledged.
2
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76
S. Reiman et al. · 3-Pyrenylacrylates
[
[
[
[
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