Synthesis and Electronic Properties of Novel 5,7-Diazapentacene Derivatives

Article abstract of DOI:10.1002/chem.201805466

A route to the synthesis of novel 5,7-diazapentacenes and some preliminary studies on their properties is reported. A single crystal X-ray diffraction study of the dihexyl derivative showed it had formed a dimer during the analysis. The materials possess lower lying frontier orbitals than pentacene and may have potential applications in organic electronic devices. This synthetic method may be applicable to the synthesis of other azaacenes.

Full text of DOI:10.1002/chem.201805466

A Journal of
Accepted Article
Title: Synthesis and electronic properties of novel 5,7-diazapentacene
derivatives
Authors: Andrey Lunchev, Samuel Morris, Rakesh Ganguly, and
Andrew Clive Grimsdale
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Synthesis and electronic properties of novel 5,7-diazapentacene
derivatives
Andrey V. Lunchev,a Samuel A. Morris,a Rakesh Ganguly,b and Andrew C. Grimsdalea†
Si(iPr)3
Ph Ph
Abstract: A route to the synthesis of novel 5,7-diazapentacenes and
some preliminary studies on their properties is reported. A single
crystal X-ray diffraction study of the dihexyl derivative showed it had
formed a dimer during the analysis. The materials possess lower lying
frontier orbitals than pentacene, and may have potential applications
in organic electronic devices. This synthetic method may be
applicable to the synthesis of other azaacenes.
X
X
X
X
1
Ph Ph
2
C6H13
R
R
1
13
6
11
8
C6H13
2
3
X = CH
X = N
10
9
12
3
4
14
N
5
N
7
Si(iPr)3
N
N
4
7
R = H
R = C
R = Ph
C6H13
C6H13
5
6a
6H13
6b
C6H13
C6H13
N
N
N
N
H3CO
OCH3
OCH3
9
OCH3
8
Introduction
Figure 1. Structures of acenes and azaacenes, their precursors and derivatives.
1
Acenes are one of the most heavily investigated classes of
the octahydroacene 7.9 However, all attempts to dehydrogenate
7 or the dibenzotetrahydroderivative 8 were unsuccessful. We
were able to synthesize a 5,7-diazapentacene derivative 9
bearing additional benzene rings by means of a Friedländer
reaction followed by oxidation. We now report a synthesis of 5,7-
diazapentacenes bearing hexyl (6a) and phenyl (6b) substituents
organic semiconductors, due to the exceptionally high (>10
cm2/Vs) charge carrier mobilities measured in single crystals of
these materials such as pentacene (1) and rubrene (2).2 Charge
carrier mobilities above 1 cm2/Vs have also been measured in
field effect transistors (FETs) using thin films of solution
processable pentacene derivatives such as TIPS-pentacene (3).
by
a
reaction between aryldiaminodiketones and
a
3
While these acenes are p-type materials, the incorporation of
phenyliodonium salt.
nitrogen atoms into the aromatic core of acenes such as
pentacene increases their electron affinity and lowers the frontier
molecular orbital energies, making them better electron acceptors
and transporters. As a result, tetraazapentacene analogues of
TIPS-pentacenes such as 4 are n-type semiconductors.4 Thus,
pyrazinacenes such as 4 which contain pyrazine rings have
become widely studied materials due to their potential application
as n-type semiconductors in OFETs and other organic electronic
devices,1 and there exist well developed procedures for their
synthesis.5-7
However, some nitrogen doped acenes, which could be important
for elucidating structure-property relations such as 5,7-
diazapentacene (quinolino[3,2-b]acridine) (5), have never been
synthesized, and, thus, studied. The only reported attempt to
synthesize 5 was unsuccessful.8 In our previous report, we tried
to obtain the 12,14-dihexyl derivative 6a by means of a
Friedländer reaction followed by dehydrogenation of
Results and Discussion
Synthesis of 5,7-diazapentacene derivatives
We found that the diaminodiketone 10, whose synthesis was
previously reported by us,9 reacts with diphenyliodonium triflate10
in the presence of catalytic amounts of copper (I) iodide in 1,2-
dichloroethane (DCE) at 70 °C, to give the 5,7-diazapentacene 6a
in 30% yield. (Scheme 1).
The derivative 6b bearing phenyl groups was synthesized
employing the strategy shown in Scheme 2. First, 1,5-dimethyl-
2,4-dinitrobenzene 11 was obtained by means of nitration. Then
11 was oxidized to the diacid 12 using CrO3 11 followed by Friedel-
Crafts reaction between the acid chloride and benzene in 1,1,2,2-
12
tetrachloroethylene (TCE)
to give 13 in 61% yield. The
reduction of 13 by hydrogen at atmospheric pressure in presence
of Pd/C gave the desired diaminodiketone 14 in 86% yield. The
reaction of 14 with two equivalents of diphenyliodonium triflate
leads to the 5,7-diazapentacene 6b in 55% yield.
The structures of the products 6a,b were determined by means of
1H and 13C NMR, and High Resolution Mass Spectrometry
(HRMS).
[a]
[b]
School of Materials Science and Engineering, Nanyang
Technological University, 50 Nanyang Avenue, Singapore 639798
Division of Chemistry & Biological Chemistry, School of Physical &
Mathematical Sciences, Nanyang Technological University,
Singapore 637371
†
Author to whom correspondence should be addressed
acgrimsdale@ntu.edu.sg
C6H13
C6H13
C6H13
C6H13
O
2 [Ph
2I]OTf
CuI (20 mol%),
C2H4Cl
O
Supporting information for this article is given via a link at the end of
the document
N
N
, 30%
H2N
NH2
2, 70°C, 12h
10
6a
Scheme 1. Synthesis of 5,7-diazapentacene 6a.
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10.1002/chem.201805466
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O
O
HO
O2N
OH
HNO3
CrO3
H2SO4
H2SO4
NO2
, 60%
O2N
NO2
50%
NO2
12
11,
1) SOCl2
,
H6
2) C6
AlCl
3, TCE
O
O
O
O
Pd/C,
H
(1 atm)
2Ph2IOTf
CuI (20mol%)
Ph
Ph
NH2
2
Ph
Ph
DCM/MeOH
DCE, 73°C
H2N
O2N
NO2
, 61%
N
N
14
, 86%
13
6b
, 55%
Scheme 2. Synthesis of 6b.
The Single Crystal XRD (SCXRD) data obtained from crystals
grown from a solution of 6a in 1,2-dichlorobenzene suggests the
formation of a dimer (Figures 2, 3 & 4). Figure 2 (top) shows a
truncated single dimer molecule of compound 6a where the C6H13
tails attached to the opposite ring carbon from each nitrogen have
been removed for clarity. Hydrogen bonds can be observed as
dashed lines; it is these favorable hydrogen bonds which we
believe encourage the nitrogen atoms to remain on the same face
during dimerization. SCXRD shows the dimer of compound 6a
stacks parallel to the b-axis (Figures 2 & 3) with all nitrogen
atoms on the same side of the molecule. The four nitrogen atoms
hydrogen bond with two symmetry-equivalent waters of
crystallization, which in turn hydrogen bond to a second water of
crystallization. This is unlike our previously reported dimer of
tetrahydro-5,7-diazapentacene derivative 8,9 (Figure 2 bottom),
which does not crystallize with any water in the structure, and in
which the nitrogen atoms in the two units are on opposite sides of
the molecule. This indicates that with water in the crystal, the
favorable formation of hydrogen bonds encourages the pyridine
groups to align in the same direction. By contrast in the dimer of
8 they align in opposite directions, presumably to cancel out the
dipoles within the pyridine rings.
Figure 3. This shows how the x-shaped dimers interconnect in the a-c plane.
The long C6H13 chains extend to interact with each other through van de Waals
forces. A single unit of the dimer has been highlighted in yellow. The image
shows a 2x2x2 supercell of compound 6a viewed down the b-axis where and
the unit cell is shown as blue dashed lines.
Figure 4: A ‘side-on’ view of how the dimer stacks parallel to the b-axis. The
relationship between the waters of crystallization and the nitrogen from the
pyridine rings are also clearly shown.
R
R
The dimerization of 6a prohibits π-π interactions between
neighboring molecules, instead, neighboring molecules
predominantly interact through van de Waals forces from the long
extending C6H13 units as can be seen in Figure 4.
N
N
R
R
The formation of such dimers, sometimes referred to from their
shape as ‘butterfly dimers’, is well known for pentacene
derivatives.13 If, as was originally assumed, it involves a concerted
[4+4] cycloaddition it is photochemically allowed but thermally
forbidden. However, thermally activated dimerizations of
terminally substituted pentacenes have been reported,13c and
theoretical investigations suggest that it may instead involve a
biradical intermediate.14 The formation of the dimer is favoured by
the absence of oxygen as in the presence of oxygen, oxidative
decomposition (probably involving an endoperoxide intermediate)
is favoured.
N
N
dimer of 6a
N
N
R
R
R
R
N
N
The bond lengths between the units in the dimer were 1.620(6) Å
for the C2-C2 bond and 1.636(6) Å for the C5-C5 bond. These
values are within an acceptable uncertainty of 0.02 Å from each
other, and from values of 1.618(3) Å for the dimer of 8 previously
reported by us,9 and 1.604(2) for a pentacene dimer.13a
We have not been able to definitively establish whether the
dimerization happens during XRD measurements or during the
crystal growth. The absence of any signals from the dimer in the
NMR spectra or mass spectra of 6a, and the formation of a dimer
dimer of 8
Figure 2. (top) A truncated single dimer molecule of compound 6a. Carbon,
oxygen, nitrogen and hydrogen are shown as black, red, blue and pink spheres
respectively. Hydrogens attached to the carbon backbone have been removed
for clarity. The same colouring scheme is followed throughout the other XRD
images. (Bottom)
comparison.9
A similarly truncated single dimer molecule of 8 for
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during an XRD experiment for a similar molecule (8) reported
previously by us suggests that dimerization happens upon the
incorporation of nitrogen atoms into the pentacene aromatic
system lowers the energy levels of the frontier orbitals.
These results suggest that 5,7-diazapentacene derivatives might
have potential applications in n-type or ambipolar transistors as
has been found for 1,8- and 1,11-diazapentacenes.17 Samples of
6a and 6b have been supplied to collaborators to investigate more
fully their electrical properties.
9
exposure to X-Ray radiation. Supporting this, the crystals
supplied for the XRD experiment were purple but the crystal used
appeared colourless after the XRD experiment. UV irradiation of
6a either in solution or the solid state did not result in formation of
the dimer, but appeared from NMR and mass spectral data to
mainly produce partial decomposition of the molecule, though a
weak signal corresponding to the mass of the dimer was observed
in the mass spectrum. We did not succeed in growing single
crystals of 6b suitable for SCXRD analysis due to its low solubility
in organic solvents. It was noted that samples of 6b left in the light
for several days started to become colorless, which NMR and
mass spectral analysis suggested was largely the result of partial
decomposition, with only a weak signal corresponding to a dimer
being seen in the mass spectrum. This suggests 6b is less stable
than 6a. A sample of 6b in CD2Cl2 – CF3COOD showed no sign
of decomposition after several days exposure to light, suggesting
acid may stabilize these molecules. Further experimental and
theoretical investigation will be required to fully explain the
formation of the dimer of 6a. If a way can be found to produce
significant quantities of the dimer it would be interesting to study
its binding with metal ions. Further exploration of the ability of
water molecules to direct the direction of stacking is another area
of future research which might produce interesting results.
1,6
6a
6b
1,4
1,2
1,0
0,8
0,6
0,4
0,2
0,0
-0,2
300
400
500
600
700
800
Wavelength (nm)
Figure 5. UV-Vis absorption spectra of 6a (black) and 6b (red)
Electronic properties
The optical absorption spectra of 6a and 6b are shown in Figure
5. Both the spectra exhibit very similar pattern, with a slight red
shift of the signals for 6b. The values of ꢀꢁꢂꢃ and ꢀꢄꢅꢆꢇꢈ are given
in Table 1. Based on these values, the compounds have a band
gap ꢉꢊ of 1.7 for 6a, and 2.0 for 6b. Unlike 7, 6a and 6b
demonstrate no fluorescence and are black colored solids.
Samples have been supplied to collaborators for more detailed
investigations of their optical properties.
6a
6b
Both 6a and 6b demonstrate two irreversible reductive and
+
oxidative peaks in CV using FeCp2/FeCp2 as internal standard
-1,5
-1,0
-0,5
0,0
0,5
1,0
1,5
Potential (V)
(Figure 6) from which their HOMO and LUMO energy levels were
calculated using the following equations:15
Figure 6. CV plots for 6a (black) and 6b (red) scanned at 50 mV/s.
Table 1. Optical, electrochemical, and electronic properties of 6a,b.
ꢉ ꢋꢌꢍꢌ = −(ꢉꢄꢄꢃꢅꢆꢇꢈ(ꢎꢏ. ꢐꢑꢒꢓ2/ꢐꢑꢒꢓ2+) + 5.10)
(
)
ꢉ ꢔꢕꢍꢌ = −(ꢉꢖꢄꢇꢅꢗꢆꢇꢈ(ꢎꢏ. ꢐꢑꢒꢓ2/ꢐꢑꢒꢓ2+) + 5.10)
(
)
They exhibit very close values of oxidation potentials of 0.4 and
0.6 V corresponding to HOMO energies of -5.2 and -5.4 eV
respectively. The values of reduction potentials are -1.3 V and -
1.4 V corresponding to a LUMO energy value of -3.5 eV and -3.6
eV respectively. Thus, based on the results from CV, the
compound 6a has a band gap of 1.7 eV and 6b of 1.8 eV. For
comparison, the reported values for pentacene of -5.00 and -3.20
eV,16 and -5.40 and -3.40 eV for an inseparable mixture of 1,8-
and 1,11-diazapentacenes.17 Those values were calculated using
a value of -4.8 eV for FeCp2/FeCp2+ and must be lowered by 0.3
eV to be directly compared with our values.
6a
6b
ꢀꢁꢂꢃ (nm)
ꢀꢄꢅꢆꢇꢈ (nm)
429, 551
674
-1.3
0.4
-5.2
-3.5
1.7
430, 558
687
-1.4
0.6
-5.4
-3.6
1.8
ꢖꢇꢗ
ꢄꢅꢆꢇꢈ
ꢉ
vs. Fc/Fc+ (V)
vs. Fc/Fc+ (V)
ꢄꢃ
ꢄꢅꢆꢇꢈ
ꢉ
HOMO level (eV)
LUMO level (eV)
ꢉꢊ [from CV] (eV)
ꢉꢊ [Optical] (eV)
1.7
2.0
As can be seen from Table 1, the new azaacenes 6a and 6b
demonstrate similar values for HOMO and LUMO to the mixture
of 1,8- and 1,11-diazapentacenes. These results confirm that the
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10.1002/chem.201805466
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dichloromethane. The organic fraction was dried over MgSO4 and
evaporated. Column chromatography (Hex:EtOAc = 3:2) afforded 11.0 g
of the product (61% yield). %. 1H NMR (400 MHz, CDCl3) δ 9.09 (1H, s),
7.76 (4H, m), 7.66 (2H, m), 7.59 (1H, s), 7.50 (4H, m). 13C NMR (100 MHz,
CDCl3) δ 190.49, 146.86, 141.15, 134.86, 134.55, 129.62, 129.41, 129.31,
129.20, 124.78, 121.28
Conclusions
A procedure for synthesis of 5,7-diazapentacene derivatives has
been established. Such molecules are reported in literature for the
first time. Single crystal X-ray diffraction analysis of a crystal of a
dihexyl derivative revealed formation of a dimer, apparently
during the X-ray diffraction experiment. The measured optical and
electrical properties of the new materials suggest that
appropriately functionalized 5,7-diazapentacene derivatives may
be suitable for applications in organic electronic devices. The
synthetic method used may be applicable to synthesis of other
azaacenes.
(4,6-diamino-1,3-phenylene)bis(phenylmethanone) (14). A mixture of
(4,6-dinitro-1,3-phenylene)bis(phenylmethanone) (11.0 g, 29.2mmol),
2.85 g Pd/C (10% of Pd), 230ml of dichloromethane, and 110 ml of
methanol was stirred for 72 h under hydrogen (1 atm). The resulting
mixture was filtered through a pad of Celite, evaporated, and purified using
column chromatography (DCM:EtOAc = 9:1), to afford 8.0 g of the product
(86% yield). 1H NMR (400 MHz, CDCl3) δ 7.76 (1Η, s), 7.47 (4H, m), 7.37
(2H, m), 7.30 (4H, m), 6.59 (4H, br. s), 5.81 (1H, s). 13C NMR (400 MHz,
CDCl3) 197.11, 155.31, 146.46, 139.87, 130.49, 128.43, 127.90, 110.26,
98.45
Experimental Section
Reagents were purchased from Sigma-Aldrich and used as received.
Diphenyliodonium Trifliorosulfate was synthesized according to a known
procedure.[18] Chromatographic purification was performed as flash
chromatography with silica gel (40−65 μm) and solvents indicated as
eluent with 0.1−0.5 bar pressure. For quantitative flash chromatography,
technical grades solvents were utilized. Analytical thin-layer
chromatography (TLC) was performed on silica gel 60 μm F254 TLC glass
plates. Visualization was accomplished with UV light. Details of SCXRD,
UV-Vis and CV experiments, NMR, mass spectra, and SCXRD
crystallographic data are provided in the Supporting Information.
12,14-dihexylquinolino[3,2-b]acridine (6a). A mixture of 629 mg (1.9
mmol) of 1,1'-(4,6-diamino-1,3-phenylene)bis(heptan-1-one), 1.670 g (3.9
mmol) of diphenyliodonium triflate, 79 mg (0.4 mmol) of copper (I) iodide,
and 20 ml of 1,2-dichloroethane was stirred at 70°C for 12 h under nitrogen.
The mixture was quenched with 3ml of concentrated aqueous ammonia
and 10 ml of water, extracted with DCM. The organic phase was dried over
MgSO4, evaporated, then purified using column chromatography
(DCM:EtOAc:Et3N = 1:1:0.1) producing 255 mg (0.6 mmol, 30% yield) of
the product as a black powder. 1H NMR (400 MHz, CDCl3) δ 9.31 (1H, s),
9.21 (1H, s), 8.14 (2H, d, J = 9.09 Hz), 8.08 (2H, d, J = 9.09 Hz), 7.67 (2H,
m), 7.36 (2H, m), 3.72 (4H, t, J = 8.08 Hz), 1.89 (4H, m), 1.64 (4H, m), 1.47
– 1.34 (8H, m), 0.93 (6H, t, J = 7.07 Hz). 13C NMR (400 MHz, CDCl3) δ
151.43, 148.06, 146.18, 130.78, 130.67, 128.32, 125.09, 124.58, 123.97,
123.53, 121.41, 31.78, 31.63, 30.23, 28.21, 22.66, 14.05. HRMS (ESI): [M
+ H]+ calcd for C32H37N2 m/z 449.2951, found m/z 449.2955 (correct
isotope distribution). UV: λmax 429 nm, εmax 7600 L mol-1 cm-1.
1,5-dimethyl-2,4-dinitrobenzene(11)
A
literature procedure was
used.[19] 25 g (22.4 ml, 0.13 mol) of 1,5-dimethyl-2,4-dinitrobenzene were
dissolved in 60 ml of 98% H2SO4 at 15 °C. Then 12 ml of 70% HNO3 was
added within 1 h at a rate such that the temperature did not exceed 15 °C.
The reaction mixture was stirred for 1 h, poured onto the mixture of ice and
water, the resulting precipitate was filtered and washed with water. The
solid was recrystallized from methanol (100 ml) two times to produce 16.5
g of the product (50% yield). 1H NMR (400 MHz, CDCl3) δ 8.72 (1Η, s), 7.38
(1H, s), 2.70 (6H, s). 13C NMR (400 MHz, CDCl3)
δ 146.74, 138.99, 137.30, 121.79
12,14-diphenylquinolino[3,2-b]acridine (6b). A mixture of 500 mg (1.6
mmol) of (4,6-diamino-1,3-phenylene)bis(phenylmethanone), 1430 mg
(3.3 mmol) of diphenyliodonium triflate, 60 mg (0.4 mmol) of copper (I)
iodide, and 15 ml of 1,2-dichloroethane was stirred at 70 °C for 12 h under
nitrogen. The mixture was cooled down to room temperature, then 10 ml
of THF and 2ml of trimethylamine were added. The mixture was filtered,
and the black precipitate was washed with THF, then dried in vacuo.
Obtained 376 mg (0.9 mmol, 55% yield) of the product as a black powder.
1H NMR (400 MHz, CD2Cl2 + CF3COOD) δ 9.97 (1H, s), 9.10 (1H, br. s),
8.49 (2H, d, J = 3.03 Hz), 8.21 (2H, d, J = 8.84 Hz), 7.89 (2H, m), 7.78 (2H,
m), 7.69 (4H, m), 7.53 (4H, m). 13C NMR (400 MHz, CD2Cl2 + CF3COOD)
δ 144.99, 143.62, 138.29, 131.86, 131.28, 130.57, 130.51, 129.18, 128.90,
119.76, 119.10, 116.26, 113.41, 110.57, 108.49. HRMS (ESI): [M + H]+
calcd for C32H20N2 m/z 433.1699, found m/z 433.1695 (correct isotope
distribution). UV: λmax 430 nm, εmax 7200 L mol-1 cm-1.s
4,6-dinitroisophthalic acid (12). Modified literature procedure [2] was
used. A solution of 1,5-dimethyl-2,4-dinitrobenzene (15.7 g, 80 mmol) in
120ml of 98% H2SO4 was added within 2 h to a mixture of chromium (VI)
oxide (40.0 g, 400 mmol) and 140 ml of 98% H2SO4 in a rate that the
temperature did not increase above 15 °C. The mixture was stirred with
cooling until the temperature dropped to 5 °C, then it was stirred for 2 h at
room temperature. The mixture was then poured onto ice and extracted
with diethyl ether. The organic phase was collected, evaporated, dissolved
in water, filtered, washed with dichloromethane (DCM), then extracted with
diethyl ether. The drying of the solution over MgSO4 followed by
evaporation gives 12.4 g of the product (60% yield). 1H NMR (400 MHz,
DMSO-d6) δ 8.75 (1Η, s), 8.31 (1H, s). 13C NMR (400 MHz, DMSO-D6)
163.80, 148.81, 131.80, 130.67, 120.24
Acknowledgements
(4,6-dinitro-1,3-phenylene)bis(phenylmethanone)
(13).
Modified
We gratefully acknowledge funding for this research from the
Singapore Ministry of Education through the Academic Research
Fund Tier1 (grant RG117/15) and Tier2 (grant MOE2013-T2-2-
002). We thank Madame Wong Lai Kwai at Chemistry Department,
National University of Singapore for performing the high
resolution mass spectra.
literature procedure [20] was used. 12.3 (48.0 mmol) 0f 4,6-
g
dinitroisophthalic acid were mixed with 43 ml of SOCl2, then heated for
reflux until all the solid had dissolved, which took about 4 h. The excess of
SOCl2 was distilled off, after that 45 ml of 1,1,2,2-tetrachloroethane and 20
ml of benzene were added, followed by the addition of AlCl3 (27.8 g, 208
mmol) at 0°C within 40 min. The mixture was stirred overnight at room
temperature, the poured into the mixture if methanol (100 ml), ice (100 g)
and concentrated HCl (10 ml). The resulting mixture was partially
evaporated, mixed with 150 ml of water, and then extracted with
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Chemistry - A European Journal
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[9]
H. Quast, N. Schön, Liebigs Ann. Chemie 1984, 1984 (1), 133-146.
A. V. Lunchev, V. C. Hendrarta, A. Jaggi, S. Morris, R. Ganguly, X. Chen,
H. Sun, and A. C. Grimsdale, J. Mater. Chem. C 2018, 6 (14), 3715-3721.
Keywords: arenes • synthetic methods • X-ray diffraction •
dimerization • cyclic voltammetry
[10] X. Pang, Z. Lou, M. Li, L. Wen, and C. Chen, Eur. J. Org. Chem. 2015,
2015 (15), 3361-3369.
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10.1002/chem.201805466
Chemistry - A European Journal
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Title
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Andrey V. Lunchev, Samuel A. Morris,
Rakesh Ganguly, Andrew C. Grimsdale*
R
N
R
N
R
R
2 [Ph2I]OTf
O
O
CuI (20 mol%),
Page No. – Page No.
, 70°C, 12h
H2N
NH2
H
C2 4Cl2
Title Synthesis and electronic
properties of novel 5,7-
diazapentacene derivatives
A route to the previously unknown 5,7-diazapentacene skeleton has been
developed and the electronic properties of the new acenes studied.
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