Synthesis of a porphyrin-hexaarylbenzene-hexabenzocoronene triad

Article abstract of DOI:10.1142/S1088424618500451

The synthesis of a triad consisting of porphyrin and hexabenzocoronene (HBC) units, which are connected via a central hexaarylbenzene (HAB) core, is presented. The ortho substitution pattern at the core results in a close proximity of the two chromophores, which influences their properties such as the intensity ratio of UV-vis absorption bands.

Full text of DOI:10.1142/S1088424618500451

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2018; 22: 454–460
DOI: 10.1142/S1088424618500451
Published at http://www.worldscinet.com/jpp/
Synthesis of a porphyrin-hexaarylbenzene-hexabenzo-
coronene triad
Max M. Martin and Norbert Jux*◊
Department Chemie und Pharmazie & Interdisciplinary Center for Molecular Materials (ICMM),
Friedrich-Alexander-University Erlangen-Nürnberg, Nikolaus-Fiebiger-Str. 10, 91058 Erlangen, Germany
Received 5 March 2018
Accepted 21 March 2018
ABSTRACT: The synthesis of a triad consisting of porphyrin and hexabenzocoronene (HBC) units,
which are connected via a central hexaarylbenzene (HAB) core, is presented. The ortho substitution
pattern at the core results in a close proximity of the two chromophores, which influences their properties
such as the intensity ratio of UV-vis absorption bands.
KEYWORDS: porphyrin, hexabenzocoronene, hexaarylbenzene.
were observed [23–25]. So far, porphyrins attached either
INTRODUCTION
to HABs or to HBCs separately are known. However, a
Porphyrins are, due to their light harvesting properties,
combination of porphyrin, HAB and HBC within one
widely used as organic building blocks and investigated
intensively. Since the first synthesis of meso substituted
porphyrins by Rothemund in 1935 [1–4], improved
molecule has not been reported yet and therefore, we
decided to synthesize a porphyrin-HAB-HBC triad, in
which the HAB serves as a bridge between the porphyrin
synthetic protocols by Adler, Longo and co-workers [5,
and HBC.
6] as well as by Lindsey et al. [7, 8] were developed,
which allow the production of porphyrins under mild
conditions in high yields. Complex multi–porphyrin
architectures have been synthesized such as linear meso-
connected porphyrin strings with up to 24 units [9–14]
as well as cyclic porphyrin arrangements [15–21].
Furthermore, porphyrins have also been combined with
other chromophores, either indirectly or directly. For
example, hexaarylbenzenes (HABs) have been used as
an indirect linker between porphyrin and coumarin units
RESULTS AND DISCUSSION
For the synthesis of a porphyrin-HAB-HBC triad 10,
the two building blocks 4 and 8 were needed. Porphyrin
4
was prepared by a known statistical porphyrin synthesis
but using microwave radiation as a heating source
Scheme 1) [26, 27]. The AB TMS-ethynylporphyrin
(
3
was obtained in 10% yield and subsequently metallated
by stirring the free-base porphyrin with an excess of
Zn(OAc) in a CH Cl /MeOH solution in quantitative
[22]. Previously, we have worked with similar systems, in
2
2
2
which porphyrins were connected to HABs [23–25], but
in a final reaction they were transformed to the respective
yield. Finally, the TMS protection group was removed
by using TBAF as a fluorine source which yielded the
ethynylporphyrin 4 in 90% yield.
The second building block, HBC 8, was synthesized
according to modified literature procedures (Scheme 2)
hexabenzocoronenes (HBCs), therefore forming
a
chromophore. The reaction towards porphyrin-HBCs has
a significant impact on the properties of the porphyrins.
Due to the large p–system of the HBC, strong electronic
communication with the porphyrin as well as strong
intermolecular interactions in the solid state and gas phase
[
28]. Iodotolan 5 [28] and tert-butyl substituted tetra-
cyclone 6 [24] were reacted in a Diels–Alder reaction at
60°C in the microwave reactor. Iodo-HPB 7 was obtained
2
in 78% yield and converted to the corresponding HBC 8
under oxidative Scholl conditions in 98% yield.
◊
SPP full member in good standing
*
Correspondence to: Norbert Jux, tel.: +49 (0)9131-8565583,
Both building blocks 4 and 8 were reacted in
Sonogashira coupling reaction in which the
email: norbert.jux@fau.de.
a
Copyright © 2018 World Scientific Publishing Company

SYNTHESIS OF A PORPHYRIN-HEXAARYLBENZENE-HEXABENZOCORONENE TRIAD
455
t-Bu
t-Bu
1
) I2, CH2Cl2, 40 °C, µW
O
2) p-Chloranil
O
t-Bu
t-Bu
3) Zn(OAc)2 in CH2Cl2/MeOH
4)TBAF in THF
H
N
N
N
N
N
+
+
Zn
t-Bu
t-Bu
1
3
Si
t-Bu
t-Bu
2
4
Scheme 1. Synthesis of zinc-ethynylporphyrin 4
t-Bu
t-Bu
I
t-Bu
t-Bu
t-Bu
t-Bu
5
+
Ph O
FeCl3
CH3NO2
CH2Cl2
2
260 °C
O
µW
t-Bu
t-Bu
I
t-Bu
I
98 %
78 %
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
6
8
7
Scheme 2. Synthesis of iodo-HBC 8
Ar
Ar
N
N
N
Ar
N
Ar
Ar
Zn
N
Zn
N
N
N
Ar
t-Bu
Pd(PPh3)2Cl2
CuI, NEt3,
THF, 50 °C
Ph2O
60 °C
µW
2
t-Bu
t-Bu
+
+
4
8
6
32 %
50 %
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
10
Ar = 3,5-di-tert-butylphenyl
t-Bu
t-Bu
9
Scheme 3. Synthesis of porphyrin-HAB-HBC triad 10
acetylene-bridged porphyrin-HBC system 9 was formed
in 32% yield (Scheme 3). In addition to the desired
product, a homocoupling product between two porphyrins
was obtained, which explains the relatively low yield of
9. Nevertheless, 9 and 6 were successfully reacted in a
final Diels–Alder reaction in the microwave reactor and
the porphyrin-HAB-HBC triad 10 was obtained in 50%
yield.
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 455–460

456
M. M. MARTIN AND N. JUX
1
Fig. 1. H NMR Spectrum (400 MHz, CDCl , rt) and HRMS (APPI-ToF)
3
Fig. 2. Left: Calculated structure of complete molecule (semi empirical, PM6). Hydrogens are omitted for clarity. Right: DFT
(
B3LYP, 6-31G*) calculated molecular orbitals of a simplified molecular structure. Tert-butyl groups and the central zinc atom were
omitted for calculation time saving reasons
1
The H NMR (Fig. 1) shows the successful formation
were expected, and the remaining two protons come to
resonance at 7.98 ppm and 7.74 ppm. This is a significant
upfield shift compared to normal b-pyrrolic protons,
which are usually in the range of ~9 ppm [29, 30]. This
shift is due to the close proximity of the two b-pyrrolic
protons to the aromatic HBC core (see calculated structure
in Fig. 2). The protons of the aryl substituents show
of the product. The most downfield shifted signals from
.34–8.95 ppm originate from the protons attached to
the HBC and appear as six separate singlets. Further
9
upfield, the resonances of the b-pyrrolic protons generate
3
six doublets ( J = 4.7 Hz) found at 8.89–8.51 ppm with
only two of them overlapping. Due to the low symmetry
4
of the porphyrin, eight signals for the b-pyrrolic protons
up at 8.01–7.55 ppm as three doublets ( J = 1.7 Hz)
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 456–460

SYNTHESIS OF A PORPHYRIN-HEXAARYLBENZENE-HEXABENZOCORONENE TRIAD
457
4
and two triplets ( J = 1.7 Hz). The resonances of the
hydrogen atoms corresponding to the HAB part of
the molecule are shown from 7.32–6.67 ppm with the
exception of two signals, which appear more downfield
10 at 363 nm is significantly higher compared to the
reference hexa-tert-butyl-HBC (e = 150000) [31]. Addi-
tionally, a broad absorption band from ~630–850 nm
is shown, which is not present in the spectra of the
reference compounds.
3
shifted at 7.90 ppm and 7.66 ppm as two doublets ( J =
.9 Hz). These signals can be ascribed to the four protons
7
of the benzene ring which is connected to the porphyrin.
The aliphatic region shows 10 singlets from which three
originate from the HBC part of the molecule, four from
the HAB scaffold and three from the porphyrin’s aryl
substituents. Furthermore, HRMS (APPI-ToF) confirms
the presence of the product in which the measured spectrum
perfectly matches the calculated isotope pattern (Fig. 1).
The relative orientation of the porphyrin and HBC
towards the central HAB core is shown in Fig. 2. The
porphyrin is almost in the same plane as the inner HAB
benzene ring, whereas the HBC is twisted by ~60°. This
arrangement leads to a close proximity of the porphyrin to
the HBC plane, especially for the two b-pyrrolic positions
as well as for the tert-butyl groups of the aryl substituent.
Frontier molecular orbitals (HOMO, LUMO) as well
as HOMO-1 and LUMO+1 were calculated using DFT
and are located exclusively on the porphyrins, whereas
HOMO-2 and HOMO-3 are found on the HBC unit.
The UV-vis absorption spectrum (Fig. 3) shows strong
absorption features for the HBC at 347, 363 and 394 nm
as well as for the porphyrin at 423, 549 and 588 nm.
These absorption features are in the same spectral region
as reference compounds hexa-tert-butyl-HBC [31] and
tetra(3,5-di-tert-butylphenyl)zinc-porphyrin [32, 33] but
the intensity ratio is unambiguously different. Although
the porphyrin’s Soret band at 423 nm is still the strongest
absorption (e = 450000), the HBC band at 363 nm (e =
CONCLUSION
We have shown the successful synthesis of a
porphyrin-HAB-HBC triad. Due to the ortho substitution
at the central HAB core, both chromophores are in close
proximity to each other and therefore strongly interact
with each other. Although UV-vis absorption spectra
were recorded, further investigations of the photophysical
characteristics are needed in order to understand the
optoelectronic properties in more detail.
EXPERIMENTAL
Zinc-TMS-ethynyl-porphyrin 11. Four microwave
vials were prepared: each vial was charged with a
magnetic stir bar, CH Cl (20 mL), 3,5-di-tert-butylbenz-
aldehyde (327 mg, 1.50 mmol), 4-(trimethylsilyl-ethynyl)
benzaldehyde (101 mg, 0.50 mmol) and pyrrole (140 ml,
2.00 mmol). Just before the reaction started, I (50 mg,
0.20 mmol) was added to the particular vial and it was
sealed with a septum. The mixture was heated in the
microwave (20 s pre-stirring, 5 min at 40°C, max, power
100 W, cooling off — for exact conditions, see supporting
information). A flask charged with para-chloranil (1.47 g,
2 2
2
6.00 mmol) in 30 mL CH Cl was prepared and heated to
2 2
reflux.After each reaction the septum was removed and the
reaction mixture poured into the para-chloranil solution
flask. After the content of the last vial was added to the
220000) reaches almost 50% of the porphyrin’s Soret-
band absorption. The molar absorption coefficient of
Fig. 3. UV-vis absorption spectrum of 10 in CH Cl .
2
2
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 457–460

458
M. M. MARTIN AND N. JUX
flask, the reaction mixture was stirred for 30 min at 40°C.
The solvent was removed; the residue pre-purified by silica
plug filtration (CH Cl ) and the red porphyrin fraction
was precipitated via the addition of MeOH. The product
was filtered off and recrystallized from CH Cl /MeOH.
2
2
After drying in vacuo, the product was obtained as a
2
2
1
was collected. The solvent was removed, 3–4 drops of
white solid in 78.4% yield (606 mg, 0.644 mmol). H
NEt were added and the crude product was purified by
NMR (400 MHz, CDCl , rt): d [ppm] 7.14 (d, J = 8.4 Hz,
3
3
column chromatography (SiO , hexanes/CH Cl , 3:1). The
2H), 6.83 (d, J = 8.4 Hz, 4H), 6.81–6.75 (m, 6H), 6.69–
6.60 (m, 10H), 6.57 (d, J = 8.4 Hz, 2H), 1.11 (s, 18H),
2
2
2
second fraction was identified as the product. The pro-
duct was obtained as a red solid in 10.1% yield (212 mg,
1
3
1.07 (s, 27H). C NMR (101 MHz, CDCl , rt): d [ppm] =
3
0.202 mmol). Free-base porphyrin (212 mg, 0.202 mmol)
147.92, 147.57, 147.53, 140.91, 140.86, 140.78, 140.08,
138.62, 137.80, 137.76, 137.57, 135.54, 133.65, 131.09,
131.03, 129.10, 128.28, 123.42, 123.09, 90.63, 34.06,
was dissolved in 50 mL CHCl , a saturated solution of
3
.
Zn(OAc) 2 H O in MeOH (15 mL) was added and the
2
2
+
mixture was stirred under light exclusion for 18 h at rt.
The solvent was removed under reduced pressure and the
residue purified by silica plug filtration (hexanes/CH Cl ,
33.97, 31.14, 31.11. HRMS (MALDI) for C H I (M )
6
2
69
calc.: 940.4444, found: 940.4439. mp > 350°C.
Iodo-HBC 8. Iodo-HPB 7 (200 mg, 0.213 mmol,
2
2
1
0
9
6
7
9
1
1
1
1
1
9
:1). The pure product was obtained in 99% yield (222 mg,
1 eq) was dissolved in CH Cl (200 mL) and degassed
via bubbling N2 through the solution for 15 min.
2
2
1
.200 mmol). H NMR (500 MHz, CDCl , rt): d [ppm] =
3
.01–8.99 (m, 6H), 8.91 (d, J = 5.0 Hz, 2H), 818 (d, J =
.5 Hz, 2H), 8.08–8.07 (m, 6H), 7.86 (d, J = 6.5 Hz, 2H),
.79–7.77 (m, 3H), 1.50 (s, 36H), 1.50 (s, 18H), 0.39 (s,
A solution of dry FeCl (1.03 g, 6.38 mmol, 30 eq)
3
in CH NO (6.0 mL) was added via syringe and
3
2
the reaction was stirred for further 2 h at rt under
13
H). C NMR (126 MHz, CDCl , rt): d [ppm] = 150.54,
slight bubbling of N . The reaction was quenched
3
2
50.52, 150.50, 150.45, 150.43, 150.40, 150.37, 149.75,
49.73, 149.70, 148.55, 143.43, 141.78, 141.75, 134.37,
34.03, 132.66, 132.52, 132.42, 132.20, 132.06, 131.96,
31.59, 131.14, 130.34, 130.02, 129.77, 129.43, 122.75,
22.55, 122.22, 122.20, 120.98, 120.68, 119.69, 105.25,
5.20, 35.05, 32.20, 31.91, 31.62, 31.33, 0.28, -0.07.
via the addition of MeOH (50 mL). The solvent was
removed under reduced pressure and the product was
.
purified by a silica plug filtration (CH Cl , ∅3.5 cm
2
2
9 cm). Final purification was achieved by recrystallization
from CHCl /MeOH. The product was obtained as a
3
1
yellow solid in 98.5% yield (195 mg, 0.210 mmol). H
-1
-1
UV-vis (THF): l [nm] (e [M cm ]) = 405 (46800), 426
NMR (400 MHz, CDCl , rt): d [ppm] = 9.13 (s, 2H), 9.06
3
(561000), 557 (23100), 597 (11600). MS (LDI) m/z (rel.
(s, 2H), 8.97 (s, 2H), 8.83 (s, 2H), 8.67 (s, 2H), 8.53 (s,
+
13
int.) = 1110 (M , 100%). HRMS (APPI, toluene) for
C H N SiZn (M ) calc.: 1110.5726, found: 1110.5757.
mp > 350°C (decomp.).
2H), 1.94 (s, 9H), 1.89 (s, 18H), 1.78 (s, 18H). C NMR
+
(101 MHz, CDCl , rt): d [ppm] = 148.36, 148.17, 148.04,
73
84
4
3
131.70, 130.18, 129.83, 129.48, 129.38, 128.16, 123.73,
123.18, 123.10, 122.87, 119.99, 119.61, 119.51, 118.96,
118.61, 118.54, 118.36, 93.62, 35.77, 35.66, 35.53,
32.20, 32.14, 32.05. HRMS (APPI, toluene) for C H I
Zinc-ethynyl-porphyrin 4. Zinc-porphyrin 11 (378 mg,
0.34 mmol) was dissolved in 50 mL THF and a 1 M
TBAF solution in THF (1 mL, 1.00 mmol) was added. The
mixture was stirred for 90 min under light exclusion at rt,
the solvent was removed and the residue was purified by
silica plug filtration (hexanes/CH Cl , 2:1). The product
6
2
57
+
(M ) calc.: 928.3500, found: 928.3512. mp > 350°C.
Acetylene bridged porphyrin-HBC dimer 9. Iodo-
HBC 8 (20.0 mg, 21.5 mmol, 1 eq), zinc-ethynyl-
porphyrin 4 (24.6 mg, 23.7 mmol, 1.1 eq), Pd(PPh ) Cl
2
2
was obtained as a red solid in 89.7% yield (317 mg,
3
2
2
1
0
9
8
7
.305 mmol). H NMR (400 MHz, CDCl , rt): d [ppm] =
(0.8 mg, 1.1 mmol, 0.05 eq) and CuI (0.4 mg, 2.2 mmol,
0.1 eq) were dissolved in 2 mL THF and 1 mL NEt3
and degassed immediately (three times: sonication
for 1 min under vacuum, followed by a purge with N2
gas). The reaction was heated to 50°C in an oil bath for
22 h. The reaction mixture was separated by column
chromatography (SiO , hexanes/CH Cl , 2:1, ∅2.5
3
.00–8.99 (m, 6H), 8.91 (d, J = 4.7 Hz, 2H), 8.20 (d, J =
.3 Hz, 2H), 8.08–8.06 (m, 6H), 7.88 (d, J = 8.1 Hz, 2H),
.79–7.76 (m, 3H), 3.29 (s, 1H), 1.51 (s, 36H), 1.51 (s, 18H).
1
3
C NMR (101 MHz, CDCl , rt): d [ppm] = 150.61, 150.51,
3
150.48, 149.76, 148.65, 148.62, 143.84, 141.80, 134.32,
132.53, 132.40, 132.28, 131.43, 131.29, 131.09, 130.41,
130.23, 129.72, 129.64, 127.25, 122.85, 122.63, 121.27,
120.87, 119.57, 83.85, 77.99, 34.98, 31.69. UV-vis (THF):
2
2
2
.
cm 40 cm). The desired product was obtained in 32.4%
yield (12.8 mg, 6.96 mmol). As a byproduct, significant
amounts of homocoupling product of two porphyrins
-1
-1
l [nm] (e [M cm ]) = 405 (39900), 425 (512000), 557
+
1
(
1
18400), 597 (8000). MS (LDI): m/z (rel. int.) = 1037 (M ,
were obtained (13.7 mg, 6.60 mmol). H NMR (300 MHz,
+
00%). HRMS (APPI, toluene) for C H N Zn (M ) calc.:
CDCl , rt): d [ppm] = 9.24 (s, 2H), 9.20–9.12 (m, 6H),
70
76
4
3
1
036.5356, found: 1036.5342. mp > 350°C (decomp.).
Iodo-HPB 7. Iodo tolan 5 [28] (296 mg, 0.82 mmol,
eq) and tert-butyl substituted tetracyclone 6 [24]
9.10 (bs, 2H), 9.06 (s, 4H), 8.98 (bs, 2H), 8.90 (bs, 4H),
8.48 (d, J = 8.2 Hz, 2H), 8.34 (d, J = 8.1 Hz, 2H), 8.16 (d,
J = 1.8 Hz, 4H), 8.12 (d, J = 1.8 Hz, 2H), 7.83 (t, J = 1.9
Hz, 2H), 7.81 (t, J = 1.8 Hz, 1H), 2.01 (s, 9H), 1.96 (s,
18H), 1.89 (s, 18H), 1.56 (s, 36H), 1.55 (s, 18H). HRMS
1
(
(
500 mg, 0.82 mmol, 1 eq) were dissolved in Ph O
2.0 mL), purged with argon and heated to 260°C in the
2
+
microwave reactor for 12 h. The reaction mixture was
diluted with a small amount of CH Cl and the product
(MALDI, dctb) for C H N Zn (M ) calc.: 1838.9811,
1
32 132
4
found: 1838.9748. mp > 350°C (decomp.).
2
2
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 458–460

SYNTHESIS OF A PORPHYRIN-HEXAARYLBENZENE-HEXABENZOCORONENE TRIAD
459
Porphyrin-HPB-HBC triad 10. Porphyrin-HBC dimer
7. Lindsey JS, Hsu HC and Schreiman IC. Tetrahe-
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9
(12.8 mg, 6.96 mmol, 1 eq) and tert-butyl substituted
tetracyclone 6 [24] (8.5 mg, 13.9 mmol, 2 eq) were
8. Lindsey JS, Schreiman IC, Hsu HC, Kearney PC and
Marguerettaz AM. J. Org. Chem. 1987; 52: 827–836.
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dissolved in Ph O (0.25 mL) and heated to 260°C in the
2
microwave reactor for 12 h. The reaction mixture was
diluted with little CH Cl and the product precipitated via
2
2
the addition of MeOH. The product was filtered off, dried
1
and obtained in 50% yield (8.5 mg, 3.5 mmol). H NMR
(
2
8
400 MHz, CDCl , rt): d [ppm] = 9.34 (s, 2H), 9.32 (s,
3
H), 9.22 (s, 2H), 9.15 (s, 2H), 9.08 (s, 2H), 8.95 (s, 2H),
.93 (d, J = 4.6 Hz, 1H), 8.89 (d, J = 4.7 Hz, 1H), 8.81
t, J = 5.4 Hz, 2H), 8.75 (d, J = 4.7 Hz, 1H), 8.51 (d, J =
(
4
1
7
.7 Hz, 1H), 8.01 (d, J = 1.7 Hz, 2H), 7.98 (d, J = 4.7 Hz,
H), 7.96 (d, J = 1.9 Hz, 2H), 7.80 (d, J = 7.9 Hz, 2H),
.77 (t, J = 2.0 Hz, 1H), 7.74 (d, J = 4.7 Hz, 1H), 7.69
(
t, J = 1.7 Hz, 1H), 7.66 (d, J = 7.9 Hz, 2H), 7.55 (d, J =
1
7
1
1
0
3
.7 Hz, 2H), 7.35–7.25 (m, 2H), 7.18 (d, J = 8.4 Hz, 2H),
.06–6.87 (m, 10H), 6.67 (d, J = 7.9 Hz, 2H), 1.87 (s, 9H),
.83 (s, 18H), 1.57 (s, 18H), 1.51 (s, 18H), 1.44 (s, 18H),
.32 (s, 9H), 1.20 (s, 9H), 1.15 (s, 9H), 1.00 (s, 18H),
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-
1
-1
.55 (s, 9H). UV-vis (CH Cl ): l [nm] (e [M cm ]) =
2
2
47 (107000), 363 (221000), 394 (95400), 423
(
(
454000), 549 (18700), 588 (5870). MS (MALDI): m/z
rel. int.) = 2419.57 (M , 100%). HRMS (APPI, toluene/
+
+
CH Cl ) for C H N Zn (M ) calc.: 2419.3851, found:
2
2
176 184
4
2
419.3907. mp > 350°C (decomp.).
Acknowledgments
We gratefully acknowledge the funding by the German
Research Council (DFG) through the Collaborative
Research Centre SFB 953 (Synthetic Carbon Allotropes)
as well as by the German Fond der Chemischen Industrie
1
9. O’Sullivan MC, Sprafke JK, Kondratuk DV, Rinfray
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Supporting information
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H NMR, MS and HRMS spectra as well as detailed
conditions for microwave reactions are given in the
supplementary material. This material is available free of
charge via the Internet at http://www.worldscinet.com/
jpp/jpp.shtml.
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