Mono-functionalized dibenzo[g,p]-chrysenes for cascade energy transfer

Article abstract of DOI:10.1016/j.tetlet.2013.04.073

3-Bromodibenzo[g,p]chrysene has been synthesized in a one-pot reaction using phenyliodine(III) bis(trifluoroacetate) (PIFA) as an oxidant and a Lewis acid. The bromo function was easily converted to the cyano, alkyne, and formyl derivatives. Bodipy dyes h

Full text of DOI:10.1016/j.tetlet.2013.04.073

Tetrahedron Letters 54 (2013) 3388–3393
Contents lists available at SciVerse ScienceDirect
Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Mono-functionalized dibenzo[g,p]-chrysenes for cascade energy transfer
⇑
Elodie Heyer, Raymond Ziessel
Laboratoire de Chimie Organique et Spectroscopie Avancées, ICPEES–LCOSA, UMR 7515, 25 Rue Becquerel, 67087 Strasbourg Cedex 2, France.
a r t i c l e i n f o
a b s t r a c t
Article history:
3-Bromodibenzo[g,p]chrysene has been synthesized in a one-pot reaction using phenyliodine(III) bis(tri-
fluoroacetate) (PIFA) as an oxidant and a Lewis acid. The bromo function was easily converted to the
cyano, alkyne, and formyl derivatives. Bodipy dyes have either been constructed from the chrysene–alde-
hyde or by cross coupling reactions with the chrysene ethynyl derivatives. The linking of diketopyrrolo-
pyrrole (DPP) fragments was realized using the chrysene–ethynyl compound or with the in situ prepared
chrysene–borolane derivatives. The novel chrysene dyes are highly fluorescent in apolar solvents and
were used as input energy in intramolecular energy transfer processes with covalently linked DPP or Bod-
ipy dyes. All mixed dyes are redox active and each module is clearly identified by its redox behavior. Little
electronic interaction is evidenced whatever the nature of the dyes and spacer.
Received 13 March 2013
Revised 12 April 2013
Accepted 16 April 2013
Available online 24 April 2013
Keywords:
Chrysene
PIFA
Bodipy
DPP
Ó 2013 Elsevier Ltd. All rights reserved.
Energy transfer
Polycyclic aromatic hydrocarbons (PAHs) are molecules of con-
siderable importance for emerging technologies concerning molec-
ular electronics, optoelectronics, energy conversion devices, and
various other forms of nanotechnology.1–3 Commonly encountered
examples include triphenylenes composed of four fused benzene
rings,4 corannulenes with five fused benzene rings,5 coronenes
made from seven benzene rings,6 and hexa-peri-benzocoronenes
(HBC) consisting of thirteen fused six membered rings.7 Deriva-
tives of HBC with long alkyl chains self-organize in discrete colum-
nar mesophases which have been used in organic solar cells.8 HBC
derivatives with various patterns of substituents have proved valu-
able for the synthesis of large graphene-like sheets of particular
symmetries,9 although in most cases the construction of these edi-
fices required several synthetic steps involving multiple C–C bond
formation.
Of other PAHs, dibenzophenanthrenes and dibenzo[g,p]chryse-
nes, with, respectively, five and six benzene rings, are of particular
interest because several examples are known where a functional
group suited for postfunctionalization is present.10 Their optical
properties (e.g., high fluorescence in solution, well defined and
sharp optical transition in the near-UV)9 are similar to those of
units such as fluorene, pyrene, and perylene which we have used
previously11 as input-energy centers in multi-chromophoric dyes
to promote internal energy transfer, to concentrate photons, and
to obtain large virtual Stokes shifts.12 Such small, planar PAH
groups are disadvantageous in that they induce low solubility in
polar solvents, while twisted PAH groups such as dibenzochryse-
nes provide improved solubility but are usually rather difficult to
functionalize. While it has been recently found that unsubstituted
or tetrasubstituted chrysene molecules can be prepared from tetra-
arylethylenes using DDQ as an oxidant,10 introduction of a bromo
substituent favors the formation of phenanthrene derivatives at
the expense of chrysene because of the high oxidation potentials
of the bromo-tetraarylethylene substrates. A variety of oxidants
(FeCl3, CuCl2/AlCl3, MoCl5, SbCl5,
hm
/I2Á Á Á) can be used in place of
DDQ to catalyze aryl–aryl coupling reactions.13
We previously succeeded in using phenyliodine(III) bis(trifluo-
roacetate) (PIFA) in conjunction with a Lewis acid to promote C–
C coupling of Bodipy monomers.14,15 PIFA has also been used to
prepare meso–meso-linked linear arrays of porphyrins,16 and fused
diporphyrin scaffoldings,17 in the presence of a Lewis acid or a flu-
oroalcohol as solvent.18 Thus, we were attracted to the use of PIFA
as an oxidant for substituted tetraarylethylene derivatives and de-
scribe herein its novel application in the preparation of 3-bro-
modibenzo[g,p]chrysene in a one pot reaction. This compound
was of interest for the preparation of a series of derivatives suitable
for the introduction of various complex substituents leading to
possible applications.
When compound 1, prepared as described in the literature,19
was treated with PIFA in the presence of the Lewis acid BF3.OEt2,
the target mono-bromochrysene 3, characterized by its mass spec-
trum [EI-MS m/z 406.0 (100) and 408.0 (95)], was isolated in 21%
yield (Scheme 1). Under these conditions, a more polar dimeric
phenanthrene compound 4 was also isolated in 11% yield and char-
acterized by its mass spectrum [EI-MS m/z 816.0 (100) and 817.0
(60)]. Various isomeric forms other than that shown are possible
for this dimer. Interestingly, such dimeric phenanthrene com-
⇑
Corresponding author. Tel.: +33 03 6885 2689; fax: +33 03 6885 2761.
E-mail address: ziessel@unistra.fr (R. Ziessel).
URL:
http://icpees.unistra.fr/chimiefonctionnelle-spectroscopie-et-reactivite/
chimie-organique-et-spectroscopies-avancees/ (R. Ziessel).
0040-4039/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetlet.2013.04.073

E. Heyer, R. Ziessel / Tetrahedron Letters 54 (2013) 3388–3393
3389
lower field positions (Fig. 1). The 1H spectrum shows a diagnostic
doublet (d = 8.80 ppm, 1H, 4J = 2.0 Hz) and two overlapping multi-
plet signals (d = 7.58–7.71 ppm, 7H and d = 8.48–8.69 ppm, 7H)
indicative of two broadly distinct environments. Oxidation leading
to five-membered rings was not observed. 2D COSY and 2D NOESY
experiments confirmed the molecular structures and provided
assignments of all protons (see ESI).
Br
Br
O
+
2
i)
In considering the modification of the chrysene core to promote
functionalization such as linking the module to other chromo-
phoric units, for example borondipyrromethene (Bodipy) or dike-
topyrrolopyrrole (DPP), or to induce properties such as triplet
formation, it may be noted that chrysene substitution has not been
utilized much due to the lack of general synthetic procedures. The
objectives here were therefore to develop a battery of methods
suitable for introducing various types of functionalities (alkyne, cy-
ano, formylÁ Á Á).
Br
Br
3, 21%
ii) or iii)
Br
+
1
To this end, we first explored the synthesis of derivatives 5 and
6 using well established protocols.21 Cross-coupling with TMS–
acetylene followed by deprotection under basic conditions pro-
vided the terminal alkyne 6 in 72% yield in two steps. A cyanation
reaction,22 catalyzed by Pd, NaCN, and Zn enabled replacement of
the bromo group in 3 by a cyano function in 7 (72% yield). Further-
more, metallation of 3 at low temperature followed by formylation
with methylformate afforded the formyl derivative 8 in 60% yield
(Scheme 2). A strategy based on a carboformylation reaction23
was even more successful, reaching isolated yields of 76%.
Our next target became the construction of a Bodipy dye around
the chrysene core. The Bodipy dye 9 was prepared in three steps by
reaction of the chrysene carbaldehyde 8 with 2,4-dimethylpyrrole
in the presence of TFA to provide the dipyrromethane intermedi-
ate, followed by DDQ oxidation to the dipyrromethene and boron
complexation under basic conditions. The highly fluorescent or-
ange-red dye was isolated in 32% yield (Scheme 3). Another path-
way examined was to cross-couple the terminal alkyne 6 with a
preformed Bodipy A (Chart 1) using Pd catalysis. This provided a
quantitative yield of the dyad linking the previously unknown
chrysene derivative to a well-known Bodipy dye.
4, 11%
Br
Scheme 1. Reagents and conditions: (i) (a) Diphenylmethane (1.2 equiv), n-BuLi
(1.1 equiv), THF, 0 °C for 1 h; (b) 4-Bromobenzophenone (1 equiv), THF, À78 °C for
3 h, then rt for 15 h; (c) p-TsOH (0.2 equiv), toluene, reflux, Dean–Stark apparatus,
3 h; (ii) BF3ÁOEt2 (20 equiv), PIFA (2.6 equiv), compd 1 (1 equiv), CH2Cl2, 0 °C or (iii)
MsOH (large excess), PIFA (2.8 equiv), compd 1 (1 equiv), CH2Cl2, 0 °C, 33% of 3.
pounds have also been isolated during oxidative cyclization of
bis(biaryl)acetylene derivatives.20 Switching from BF3.Et2O to large
excess of methanesulfonic acid increased the formation of 3 to 33%
without formation of dimer 4.
Formation of the phenanthrene derivative 210 during the course
of the reaction was observed by TLC. Molecular structures were as-
signed by means of NMR spectroscopy (2D COSY and 2D NOESY in
particular) and use of compounds 1 and 2 as reference. The spec-
trum of 1 shows a typical AB system for the protons of the 4-bromo
substituted phenyl (3J = 8.4 Hz), with slight shifts (d = 6.88 and
7.23 ppm) from the other aromatic proton peaks (d = 7.36 ppm).
The regioselectivity (formation of a six- rather than a five-mem-
bered ring) of the oxidation leading to 2 is consistent with other
observations.10 The peaks in the spectrum of 2 are shifted down-
field compared to those of 1, the bromophenyl AB system, for
example, appearing at d = 7.05 and 7.39 ppm. After the two succes-
sive oxidations leading to 3, all peaks are shifted to significantly
Diketopyrrolopyrrole dyes are of particular interest in that their
absorption properties can be tuned over a large range and they dis-
X
5, 79% X = TMS
6, 91% X = H
ii)
i)
CN
Br
iii)
7, 72%
iv)
3
CHO
8, 76%
Scheme 2. Reagents and conditions: (i) [Pd(PPh3)4] (6 mol %), 3 (1 equiv), trimeth-
ylsilylacetylene (1.9 equiv), toluene, Et3N, 80 °C, 15 h; (ii) K2CO3 (8 equiv), THF/
MeOH, 20 °C, 15 h; (iii) freshly prepared catalyst,22 3 (1 equiv), NaCN (1.1 equiv), Zn
(0.5 equiv), THF, 70 °C, 2 days; (iv) for the metallation: (a) 3 (1 equiv), n-BuLi
(1.04 equiv), THF, À60 °C, 45 min, (b) methylformate (excess), À60 °C then rt, 3 h;
for the carboformylation: [Pd(PPh3)2Cl2] (9 mol %), 3 (1 equiv), sodium formate
(6 equiv), CO flow, DMF, 100 °C, 16 h.
Figure 1. 1H NMR, 300 MHz, in CDCl3 (S) for compounds 1–3.

3390
E. Heyer, R. Ziessel / Tetrahedron Letters 54 (2013) 3388–3393
F
N
B
N
H
CHO
F
Cmpd B
i)
i) ; ii)
iii)
O
N
S
S
N
O
8
9, 32%
6
O
11, 69%
O
H
O
O
N
B
Cmpd A
iv)
O
B
N
Br
O
ii)
6
10, 99%
3
iii)
Cmpd B
Scheme 3. Reagents and conditions: (i) 2,4-dimethylpyrrole (3.1 equiv),
8
(1 equiv), TFA (1.1 equiv), CH2Cl2, 30 °C, 14 days; (ii) DDQ (1 equiv), 30 °C, 5 min;
(iii) Et3N (6 equiv), BF3ÁOEt2 (8 equiv), rt, 1 h; (iv) A (0.9 equiv) and 6 (1 equiv),
[Pd(PPh3)4] (5 mol %), toluene, Et3N, 65 °C, 15 h.
O
N
S
S
N
O
I
12, 16%
O
N
Scheme 4. Reagents and conditions: (i) 6 (1 equiv) and B (0.9 equiv), [Pd(PPh3)4]
(7 mol %), toluene, Et3N, 80 °C, 15 h; (ii) (a) 2 (1 equiv), n-BuLi (1.1 equiv), THF,
N
N
À78 °C,
5 min;
(b)
2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
B
S
Br
S
(1.2 equiv) in THF, À78 °C for 5 min then rt for 30 min; (iii) B (0.9 equiv), K2CO3
N
O
(2.5 equiv), H2O (one drop), Pd(PPh3)4 (12 mol %), 80 °C, 5 days.
O
O
O
O
60,000–70,000 MÀ1 cmÀ1 range. In all cases, a weaker absorption
A
B
peak at 360 nm (
e
ꢀ 19000 MÀ1 cmÀ1) is evident. All these deriva-
tives have similar energy gaps and their absorption spectra are in
keeping with those of chrysene derivatives previously described.27
Derivatives 5–8 are fluorescent in cyclohexane solution. A max-
imum of 18% quantum yield was determined for the cyano-chry-
sene derivative 7 under anaerobic conditions. In the case of the
aldehyde derivative 8 the fluorescence is markedly weaker due
Chart 1.
play outstanding charge carrier properties which have been
exploited in the engineering of solar cells.24 Cross linking the chry-
sene alkyne 6 to the mono-bromothiophene–DPP is easily realized
under experimental conditions used for the Bodipy dyad described
above. The chrysene–DPP dyad 11 was obtained in 69% yield after
standard purification procedures. It has previously been estab-
lished that the nature of the spacer linking different modules has
a strong influence on the spectroscopic, electrochemical, and mor-
phological properties of hybrid systems.25 We tried to link the
chrysene core to a DPP module directly by a C–C bond (compound
12 in Scheme 4). The chrysene–borolane derivative appears to be
unstable and is thus very difficult to prepare, isolate, and purify.
After some experimentation, we succeeded in preparing the mixed
dye 12 by cross-coupling the in situ prepared borolane to the pre-
cursor B under standard Suzuki–Miyaura cross coupling reaction.
The poor isolated yield is mostly due to the degradation of the
borolane during the heating procedure. As well, the in situ forma-
tion of the trifluoroborate potassium salt26 limits the efficiency of
the coupling reaction.
to the presence of n?
p
⁄ transition deactivating the excited state
by non-radiative processes.28 In most cases, the emission profile
mirrors the transition lying at lower energy, which is clear evi-
dence for a localized singlet excited state. The Stokes shifts are rel-
atively modest, lying in the 2600 to 3200 cmÀ1 range, but in all
cases the excitation spectrum matches the absorption spectrum,
excluding formation of aggregates at these solution concentrations.
The hybrid dyes bearing a Bodipy residue linked to chrysene
either directly (9), or through a tolane spacer (10) exhibit absorp-
tion spectra which are almost linear combinations of the absorp-
tion bands of the individual modules (Fig. 3a and b). This
indicates weak electronic interaction between both modules, a sit-
uation expected in light of the presence of the methyl groups on
the Bodipy core which force the aromatic ring to be almost orthog-
onal to it. This arrangement has been found in several X-ray struc-
tures.29 The low energy transition at 500 nm corresponds to the
S0?S1 transition of the Bodipy fragment, while its S0?S2 transition
is localized beneath the low energy absorption of the chrysene
moiety. This is a situation extremely favorable for energy transfer,
as previously established with pyrene hybrids.11 Irradiation at
300 nm (9) and 305 nm (10) in the chrysene absorption band did
The electronic properties of these chrysene derivatives were
examined by UV absorption in deaerated cyclohexane solutions
(Fig. 2). The absorption spectra exhibit large and structured bands
between 220 and 320 nm with molar extinction coefficients in the

E. Heyer, R. Ziessel / Tetrahedron Letters 54 (2013) 3388–3393
3391
70000
60000
50000
40000
30000
20000
10000
0
a
80000
b
70000
60000
50000
40000
Absorption
Emission
Excitation
30000
20000
10000
0
Absorption
Emission
Excitation
220
320
420
520
220
320
420
520
λ (nm)
λ (nm)
c
70000
60000
50000
40000
30000
20000
10000
0
70000
60000
50000
40000
30000
20000
10000
0
d
Absorption
Emission
Excitation
Absorption
Emission
Excitation
220
320
420
520
220
320
420
520
λ (nm)
λ (nm)
Figure 2. Absorption, emission, and excitation spectra for 3, 5, 7, and 8 in degassed cyclohexane at 25 °C. (a) 3: Emission kex = 352 nm (D0 = 0.2852). (b) 5: Emission
kex = 273 nm (D0 = 0.1546); excitation kem = 401 nm. (c) 7: Emission kex = 292 nm (D0 = 0.5954); excitation kem = 442 nm. (d) 8: Emission kex = 269 nm (D0 = 0.3043);
excitation kem = 472 nm.
80000
a
100000
a
80000
60000
40000
20000
0
60000
40000
20000
0
Absorption
Excitation
Emission
Absorption
Excitation
Emission
220
420
620
240
340
440
λ (nm)
540
640
λ (nm)
b
b
60000
40000
20000
0
100000
80000
60000
40000
20000
0
Absorption
Excitation
Emission
Absorption
Excitation
Emission
230
430
630
240
340
440
540
640
λ (nm)
λ (nm)
Figure 3. Absorption, emission, and excitation spectra of dyes 9 (a) and 10 (b) in
degassed cyclohexane at 25 °C. (a) 9: Emission kex = 300 nm (D0 = 0.2656); excita-
tion kem = 550 nm. (b) 10: Emission kex = 352 nm (D0 = 0.1000); excitation
kem = 553 nm.
Figure 4. Absorption, emission, and excitation spectra of dyes 11 (a) and 12 (b) in
degassed cyclohexane at 25 °C. (a) 11: Emission kex = 310 nm (D0 = 0.3503);
excitation kem = 695 nm. (b) 12: Emission kex = 312 nm (D0 = 0.3428); excitation
kem = 613 nm.

3392
E. Heyer, R. Ziessel / Tetrahedron Letters 54 (2013) 3388–3393
monium hexafluorophosphate (TBAPF6) as supporting electrolyte
a
and the results are shown in Fig. 5a and b. They confirm that each
fragment in dyads 10 and 11 retains the redox activity of the sep-
arate modules.
Dyad 10 exhibits redox waves at +1.07 V (
À1.34 V ( Ep = 60 mV), similar to those of compound A (Fig. 5a).
The additional reversible oxidation at +1.29 V ( Ep = 60 mV) is as-
DEp = 60 mV) and
D
D
signed to the radical cation of the chrysene residue. This potential
is similar to that for the oxidation of compound 5 [+1.30 V
(D
Ep = 60 mV]. Likewise, dyad 11 exhibited three reversible oxida-
tion waves at +0.89 V ( Ep = 60 mV), +1.21 V ( Ep = 60 mV) and
+1.44 V
Ep = 60 mV), one reversible reduction at À1.15 V
Ep = 70 mV) and an irreversible additional reduction at À1.57 V
(Fig. 5b). By comparison to compound B [+0.92 V ( Ep = 60 mV),
+1.27 V ( Ep = 70 mV)] the first two oxida-
Ep = 60 mV), À1.21 V (
D
D
(D
(D
D
D
D
tion waves in 11 are safely assigned to the DPP residues and the
third to the chrysene moiety. The irreversible reduction at
À1.57 V is probably due to the reduction of the chrysene fragment
a potential close to the irreversible reduction of 5. Note that the
other redox processes appear highly reversible (ipa/ipc ꢀ 1) and ex-
b
hibit the characteristic shape (DEp = 60–70 mV) of a Nernstian,
one-electron process (Fig. 5a and b).
In summary, a convergent method has been successfully devel-
oped for the preparation of 3-bromochrysene by treatment of a
substituted tetraphenylethylene with hypervalent iodine deriva-
tive (PIFA). This new soluble molecule was efficiently converted
to alkyne, cyano, formyl, and borolane derivatives which may be
useful for the construction of sophisticated platforms. The linkage
of fluorescent Bodipy or DPP modules provided evidence of very
efficient intramolecular cascade energy transfer. Both spectro-
scopic and electrochemical measurements showed little electronic
interaction in the dyads whatever the nature of the dyes and
spacer. Ongoing work in our laboratory is now focused on selec-
tively linking such chrysene modules to phosphorescent transition
metal modules suitable for long lived triplet emission states.
Figure 5. Cyclic voltammograms of: (a) reference compound A (red trace) and
chrysene–Bodipy 10 (black trace), (b) B (purple trace), and DPP–Chrysene 11 (black
trace). Concentration of dyes 1.5 Â 10À3 M in CH2Cl2 (0.1 M, n-Bu4NPF6), Fc+/Fc
refers to the ferricinium/ferrocene couple used as internal reference E1/2 (Fc+/
Fc) = +0.38 V (DEp = 60 mV).
Supplementary data
not produce any emission of the chrysene at 402/414 nm but
exclusively emission of the Bodipy module [kem = 515 nm,
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.tetlet.2013.
04.073.
/em = 0.68, s = 3.4 ns for 9 and kem = 514 nm, /em = 0.56, s = 3.0 ns
for 10] (Fig. 3). This is clear evidence that very efficient energy
transfer from the chrysene to the Bodipy is occurring. An ultimate
confirmation was obtained by running an excitation spectrum
(kem = 553 nm); excellent agreement with the absorption spectrum
is in keeping with such a situation.
References and notes
For mixed DPP–chrysene dyes 11 and 12 the presence of the
five membered thiophene rings and the bis-lactam configuration
of the fused rings decrease the steric congestion around the
grafted subunit, allowing some electronic interactions between
the modules. This is highlighted in the absorption spectra
(Fig. 4) where the absorption band of the chrysene is broadened
by about 30 to 40 nm. The band of the DPP residue is also wider
by about 25 nm compared to the unsubstituted starting material
(reference measured in THF). Selective irradiation in the chrysene
module around 310 nm does provide emission of the DPP module
but also some residual emission of the chrysene at 417/444 nm
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s = 6.1 ns for 11 and kem = 615 nm,
/
em = 0.48, = 7.5 ns for 12] (Fig. 4). This weak residual emission
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