Gold-Catalyzed Facile Synthesis and Crystal Structures of Benzene-/Naphthalene-Based Bispentalenes as Organic Semiconductors

Article abstract of DOI:10.1002/chem.201805637

The gold-catalyzed facile synthesis of U-shaped and S-shaped bispentalenes is described from easily available tetra(arylethynyl)-benzenes and -naphthalenes. The optoelectronic and transistor properties were also investigated. The selectivity between the U-shaped and S-shaped bispentalene isomers can be tuned by the bulkiness of the ligand and the substrates. The S-shaped naphthalene-based bispentalene shows a one-dimensional face-to-face packing pattern in solid state and a good hole mobility, indicating that the S-shaped bispentalene core is highly suitable for transistor applications. The gold-catalyzed annulation of tetraynes provides a useful protocol in the synthesis of bispentalenes for organic semiconductors.

Full text of DOI:10.1002/chem.201805637

A Journal of
Accepted Article
Title: Gold-Catalyzed Facile Synthesis and Crystal Structures of
Benzene-/Naphthalene-based Bispentalenes as Organic
Semiconductors
Authors: Kohei Sekine, Jürgen Schulmeister, Fabian Paulus, Katelyn
P. Goetz, Frank Rominger, Matthias Rudolph, Jana Zaumseil,
and A. Stephen K. Hashmi
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10.1002/chem.201805637
Chemistry - A European Journal
COMMUNICATION
Gold-Catalyzed Facile Synthesis and Crystal Structures of
Benzene-/Naphthalene-based Bispentalenes as Organic
Semiconductors
Kohei Sekine,[a] Jürgen Schulmeister,[a] Fabian Paulus,[b] Katelyn P. Goetz,[b] Frank Rominger,[a]
Matthias Rudolph,[a] Jana Zaumseil,*[b] and A. Stephen K. Hashmi*[a,c]
Abstract: We describe the gold-catalyzed facile synthesis of U-
shaped and S-shaped bispentalenes from easily available
tetra(arylethynyl)-benzenes and –naphthalenes. The optoelectronic
and transistor properties were also investigated. The selectivity
between the U-shaped and S-shaped bispentalene isomers can be
tuned by the bulkiness of the ligand and the substrates. The S-shaped
naphthalene-based bispentalene shows a one dimensional face-to-
face packing pattern in solid state and a good hole mobility, indicating
that the S-shaped bispentalene core is highly suitable for transistor
applications. The gold-catalyzed annulation of tetraynes provides a
useful protocol in the synthesis of bispentalenes for organic
semiconductors.
synthesis.[9b] Obviously, one of the most step-economic strategies
for the synthesis of bis(dibenzo)pentalene is the annulation of
1,2,4,5-tetrakis(arylethynyl) benzene 1, which potentially
produces the U-shaped and S-shaped bis(dibenzo)pentalenes 2
and 3 as the second cyclization can occur onto both alkynes of
the intermediate mono(dibenzo)pentalene 4 (Scheme 1). In the
reported platinum-promoted annulation of tetrayne 1,
bispentalenes 2 and 3 were produced in poor selectivity and in
low yields.[9a] In this context, a facile synthetic method is desirable
for the supply and property evaluation of U-shaped and S-shaped
bispentalene derivatives. Recently, we reported the
(IPr)Au(NCMe)SbF6-catalyzed
annulation
of
1,2-
di(arylethynyl)benzene produced
dibenzo[a,e]pentalene
derivatives via a vinyl cation species as a key intermediate.[6o]
Herein, we present the gold-catalyzed annulation of
tetrakis(arylethynyl)-benzenes and -naphthalenes for the
synthesis of U-shaped and S-shaped bispentalene derivatives 2
and 3. The opto-electronic and transistor properties of the
obtained bispentalene derivatives are also reported.
Homogeneous gold catalysis has received much attention
in the last two decades.[1] Due to the mild carbophilic  Lewis
acidity of the gold catalyst, nucleophilic addition reactions to
unsaturated carbon-carbon multiple bonds were intensely
developed. Side–by-side gold catalysts promote the annulation of
diyne compounds, not only showing unique reaction patterns, but
also contributing to the syntheses of complicated and/or highly -
conjugated compounds.[2]
Ph
Ph
The pentalene scaffold is of high interest for materials
science due to its antiaromacity[3] as much as structurally similar
indenofluorene.[4] Due to the low stability of the pure pentalene
core,[5] the synthesis and properties of monobenzopentalene and
Ph
2
U-shaped
Ph
dibenzo[a,e]pentalene, which are stabilized by the flanking
4
1
[6]
aromatic moieties, are well studied.
Due to the promising
Ph
S-shaped
3
properties of -extended pentalenes they are attractive as organic
semiconductors.
Dinaphto[a,e]pentalene,
dianthraceno[a,e]pentalene
and
the pyrrole-fused
Scheme 1. The synthetic strategy towards bispentalenes 2 and 3.
dibenzo[a,e]pentalene exhibit high hole mobilities,[7] while the
thiophene-substitued
dibenzo[a,e]pentalenes
and
diacenopentalene dicarboximides exhibit lower-lying LUMO
First, various gold catalysts were examined with 1,2,4,5-
tetrakis((4-pentylphenyl)ethynyl)benzene 1a (Table 1). In the
presence of (IPr)AuCl/AgNTf2, 1a was completely consumed
within 30 mins to afford the U-shaped 2a in high selectivity (>20:1)
8]
levels suitable for n-type semiconductors.[6s,
Despite the
development of -extended pentalenes, the synthesis of
bispentalenes is not yet well studied.[8] The achievement of
palladium-catalyzed synthesis of bis(dibenzo)pentalenes from an
in 82% yield (Entry 1). This result matches the previous work[6g]
,
internal alkyne and bromostyrene requires
a
multi-step
where the selectivity for the U-shaped 2 was explained by the
steric hindrance of the bulky IPr ligand and the peripheral aryl
group at the second cyclization of the intermediate 4. Based on
these results, we hypothesized that if a less bulky ligand was
employed, an S-shaped bis(dibenzo)pentalene 3a might be
[a]
Dr. K. Sekine, B. Mc. J. Schulmeister, Dr. F. Rominger, Dr. M.
Rudolph and Prof. Dr. A. S. K. Hashmi
Organisch-Chemisches Institut, Heidelberg University
Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
E-mail: hashmi@hashmi.de
feasible.
As
expected,
a
smaller
carbene
ligand
[10]
(IMes)AuCl/AgNTf2 (IMes; %Vbur = 36.5, IPr; %Vbur = 45.4)
afforded the mixture of U-shaped 2a and S-shaped 3a in ratios of
82:18 in 84% combined yield (Entry 2). The isomers were
separable by silica gel column chromatography and the structures
of 2a and 3a were unambiguously confirmed by X-ray crystal
structure analysis.[11] 3a shows a one dimensional - stacking.
The acyclic carbene gold catalyst L1AuCl (%Vbur = 36.9) afforded
a 63% yield of a mixture of 64:36 2a to 3a (Entry 3).
[b]
[c]
Dr. F. Paulus, Dr. K. P. Goetz and Prof. Dr. J. Zaumseil
Institute for Physical Chemistry, Universität Heidelberg
Im Neuenheimer Feld 253, 69120 Heidelberg, Germany
E-mail: zaumseil@uni-heidelberg.de
Prof. Dr. A. S. K. Hashmi
Chemistry Department, Faculty of Science
King Abdulaziz University, Jeddah 21589, Saudi Arabia
Supporting information for this article is given via a link at the end of
the document.
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Smaller %Vbur carbene ligands, L2AuCl (%Vbur = 27.4, Entry 4)
and (IDM)AuCl (%Vbur = 26.3, Entry 5) showed a ratio of 66:34
and 55:45, respectively, though 1a remained and a relatively
complex reaction mixture was produced. These results indicate
that the selectivity for the U-shaped 2a is dependent on the %Vbur
of the applied ligands. SPhos (Entry 6), phosphite ligand L3 (Entry
7) and triphenylphosphine ligand (Entry 8) gave the isomers 2a
and 3a in ratios of 75:25, 66:34 and 50:50, respectively. The same
dependency of the selectivity as the carbene ligands was also
observed for the phosphorus ligands (Entries 6-8), underlining
that the ligand size is crucial for the selectivity.
afforded 2b and 3b in a ratio of 57:43 in high combined yields
(Entry 4). Fluoro-substituted tetrayne (1c) was converted by both
IPr and L1 ligands to 2c and 3c in high yields in a ratio of 92:8
(Entry 5) and 60:40 (Entry 6). The isomers of 2b and 3b, 2c and
3c were separable by silica gel column chromatography. The
methyl-, H-, and 4-pentylphenyl-substitutions on outer aromatic
moieties substrates 1d-1f were selectively transformed with
(IPr)AuCl to the corresponding U-shaped derivatives 2d-2f in
92%,67% and 53 yields (Entries 7, 9, and 11). With the smaller
catalyst, the pentalenes 2d and 3d (73:27), 2e and 3e (69:31),
and 2f and 3f (62:38) were produced in moderate-to-high
combined yields (Entries 8, 10, and 12). Unfortunately, in the case
of the substrates 1d-f, the two isomers 2 and 3 are inseparable
due to their poor solubility.
Table 1. Examination of different gold catalysts.
Entry[a]
Catalyst
%VBur
Time
Yield
(2a+3a)/
%
2a:3a[b]
Table 2. Gold-catalyzed synthesis of bis(dibenzo)pentalene derivatives
1
2
3
4
5
6
7
8
(IPr)AuCl
(IMes)AuCl
L1AuCl
45.4
36.5
36.9
27.5
26.3
53.7
37.8
34.8
30 min
30 min
30 min
24 h
82[c]
84
>20:1
82:18
64:36
66:34
55:45
75:25
66:34
50:50
Entry[a]
R1
R2
H
Catalyst
(IPr)AuCl
L1AuCl
Time
Yield 2/%[b]
(2:3)
63
1
2
3
4
5
C5H11
C5H11
C5H11
C5H11
C5H11
1a
1a
1b
1b
1c
30
min
82
[d]
L2AuCl
-
[d]
(IDM)AuCl
SPhosAuCl
L3AuCl
24 h
-
H
30
63[c]
min
20 h
39
37
29
Me
Me
F
(IPr)AuCl
L1AuCl
4 h
4 h
4 h
98[c]
20 h
(64:36)[d]
Ph3PAuCl
20 h
90[c]
(77:23)[d]
[a] 1a (0.05 mmol), catalysts (0.005 mmol) in solvent (1.5 mL). [b] Ratios of
2a:3a determined by 1H NMR. [c] Isolated yield of 2a. [d] Not full conversion.
(IPr)AuCl
93[c]
(57:43)[d]
6
7
8
C5H11
Me
F
1c
1d
1d
L1AuCl
4 h
95[c] (92:8)[d]
92
H
H
(IPr)AuCl
L1AuCl
1 h
Me
18 h
94[c]
(73:27)[d]
9
H
H
H
H
1e
1e
(IPr)AuCl
1 h
67
10
L1AuCl
18 h
79[c]
(69:31)[d]
Several substituents were examined next to synthesize the
U-shaped and S-shaped 2 and 3 with (IPr)AuCl or L1AuCl in
dichloromethane due to the improved solubility (Table 2). In the
case of a methyl group on the aromatic core (1b), the reaction
with (IPr)AuCl/AgNTf2 was completed within 4 h to give 2b and 3b
in 98% combined yield in a ratio of 77:23 (Entry 3). Compared to
tetrayne 1a, the reaction took longer and the ratio of S-shaped
product 3b increased. The smaller catalysts L1AuCl/AgNTf2
11
12
4-
penty-
C6H5
H
H
1f
1f
(IPr)AuCl
1 h
53
4-
penty-
C6H5
L1AuCl
18 h
58[c]
(62:38)[d]
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R
R
[a] 1 (0.05 mmol), catalysts (0.005 mmol) in solvent (1.5 mL). [b] Isolated yield.
[c] Yield of 2 and 3. [d] Ratio of 2 and 3 determined by 1H NMR.
R
R
(IPr)AuCl/AgNTf 2
(10 mol %)
DCE, rt, 2 h
Next, the gold catalytic system was applied to 2,3,6,7- and
1,2,5,6-tetra(arylethynyl)naphthalene 1g and 1h (Scheme 2 and
3). The reaction of 1g with (IPr)AuCl/AgNTf2 produced the
bispentalenes 2g and 3g in 83% yield in a ratio of 43:57 (Scheme
2). It was assumed that the poorer selectivity of 2g and 3g was
caused by the less steric repulsion of the peripheral phenyl groups
and the gold catalyst during the second annulation step. This
assumption can be underlined by a less pronounced effect for
R
R
R
R = C5H11
R
1h
5h 73% yield
Scheme 3. Synthesis of 5h.
The optical properties of bispentalenes 2a, 2c, 2g, 3a, 3c,
3g and 5h were examined by UV/Vis absorption spectroscopy
(Figure 3). TD-DFT calculations at B3LYP-d3, cc-pVTZ level of
theory (Supporting Information) suggest that the weak, broad,
long wavelength absorption (opt = 600-700 nm), which are slightly
observed in the case of 2a, 2c, 3a, 3c and 5h, can be attributed
to the symmetry-forbidden HOMO-LUMO transitions. Based on
the TD-DFT calculations, the absorptions of the second and third
longest wavelength around 500 nm and 530 nm for 2a can be
assigned to the symmetry-allowed HOMO → LUMO+1 and
HOMO-1 → LUMO transitions (Table S3). In the case of 2g and
3g only the absorptions at lower wavelengths (2g; opt = 550 and
516 nm, 3g; opt = 548 and 509 nm) are observed and the broad
absorption for the HOMO-LUMO transitions (opt = 600-700 nm)
is not detected. TD-DFT calculations suggested the
corresponding absorptions (opt = 550 and 516 nm) of 2g are
smaller carbene ligand L1 (2g:3g = 51:49). The crystal packing of
[11]
3g is shown in Figure 2.
The molecules construct a one
dimensional columnar structure (Figure 2a; viewed in the b-c
plane). Effective offset stackings between the plane cores of the
bispentalene core and
a T-shaped stacking between the
peripheral phenyl rings are observed (Figure 2b and 2c). Tetrayne
(1h) was also converted with (IPr)AuCl/AgNTf2 and selectively
afforded the corresponding bispentalene 5h in 73% yield
(Scheme 3). [11] The gold catalyst preferentially activated the less
sterically hindered alkyne at the 2- and 6-position of 5h due to the
sterically repulsion around the peri-position.
R
R
Br
Br
Pd(PPh3)2Cl2 (10 mol %)
CuI (20 mol %)
TfO
OTf
+
iPr2NH/DMF (1:1)
60 °C, 21 h, 87%
derived from the symmetry-forbidden HOMO-1
→ LUMO
C5H11
transitions (cal = 514 nm) and the symmetry-allowed HOMO →
R = C5H11
1g
R
R
6 equiv
LUMO transitions (cal = 487 nm). [12]
R
R
R
The HOMO and LUMO levels in CH2Cl2 solution were
estimated by cyclic voltammetry (Table S2). Compared to the
corresponding dibenzopentalene 6 (LUMO = -3.05 eV, Egap = 2.74
eV, Table S2) [6t], the LUMO levels of 2a (LUMO = -3.23 eV, Egap
= 1.98 eV) and 3a (LUMO = -3.23 eV, Egap = 1.99 eV) are lower
by ~0.2 eV and the HOMO-LUMO energy gap are considerably
smaller, indicating a significant effect of the -extended system
onto the LUMO level and the HOMO-LUMO gap. The fusing
pattern of the naphthalene-based bispentalenes 2g, 3g and 5h
dramatically changes the HOMO-LUMO gaps. The gap of 2g (Egap
= 2.25 eV) and 3g (Egap = 2.28 eV) is larger than that of 5h (Egap
= 1.95 eV). [12]
R
R
R
Catalysts (10 mol %)
DCE, rt, 2 h
+
R
R
2g
3g
2g 3g
(IPr)AuCl/AgNTf2 83% yield (
:
= 43:57)
L
2g 3g
1AuCl/AgNTf2
54% yield (
:
= 51:49, 24 h)
Scheme
2.
Synthesis
of
2g
and
3g
from
2,3,6,7-
tetrakis(arylethynyl)naphthalene.
Figure 2. Packing diagrams of 3g (hydrogen atoms are omitted for clarity)
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Figure 3. UV absorption of 2a, 2c, 2g, 3a, 3c, 3g and 5h.
Table 3. Transport properties of TFTs with 3g.
Peak mobility
(saturation)
(cm2V‐1s‐1)
Mobility at VGS
= ‐60 V
Threshold
voltage
(V)
Ion/Ioff
(cm2V‐1s‐1)
0.07 ± 0.03
The solid-state -stacking of the S-shaped bispentalenes 3a
and 3g indicates that they could display semiconducting behavior,
inspiring us to fabricate field-effect transistors (FETs). The zone-
casting method is suitable for film fabrication due to the one-
dimensional nature of the crystal structures, as this method is
known to yield arrays of aligned crystalline ribbons under proper
processing conditions.[13] For the molecule 3g, a slow casting
speed of 0.2 mm·s-1 on substrates of silicon/silicon
dioxide/benzocyclobutene (BCB) results in “feathered” ribbons
aligned at the micro scale, as seen in both optical and atomic
force microscopy (AFM) images (Fig. 4a, 4b). The application of
similar casting conditions to 3a results in films with an amorphous
appearance. The evaporation of gold source/drain electrodes to
form a bottom gate, top contact FET geometry (inset of Fig. 4c)
allows for hole injection and accumulation in 3g. Representative
transfer and output characteristics are shown in Fig. 4c, d, and
average device parameters based on 75 devices with different
channel lengths are shown in Table 3. The hole mobility (μ),
determined for the saturation regime using the gradual channel
approximation, exhibits moderate gate voltage (VGS) dependence,
ranging from approximately 0.1 cm2V-1s-1 at the turn-on point to a
minimum of 0.07 cm2V-1s-1 at the end of the measurement range.
The maximum mobility achieved was 0.25 cm2V-1s-1. The origin of
the gate-source voltage dependence is unknown and currently
under investigation. Nonetheless, these results suggest that the
core of the molecule is highly suitable for transistor applications,
and may show more ideal performance and higher charge-carrier
mobility upon exchange of the solubilizing groups.
0.13 ± 0.05
‐20 ± 4
105
In conclusion, we developed a convenient synthetic method
for U-shaped and S-shaped bispentalenes from readily available
tetra(arylethynyl)-benzenes/-naphthalenes. Carbene ligands are
suitable for the annulation reaction and the bulkiness of the ligand
has a significant effect on the ration between the two U-shaped
and S-shaped isomers. The S-shaped 3a and 3g showed a one-
dimensional face-to-face packing pattern. The -extended
bispentalene is effective for the shrink of the HOMO-LUMO
energy gap. Evaluation of the transistor property revealed that S-
shaped 3g shows a reasonable hole mobility (0.1 cm2V-1s-1) and
the bispentalene core is highly suitable for transistor applications.
Further applications based on the bispentalene structure are
under investigation.
Acknowledgements
The authors are grateful to funding by the DFG (SFB 1249-
NHeteropolyzyklen als Funktionsmaterialien). We thank Michael
Töpper of Fraunhofer IZM, Berlin, Germany, for generously
providing us with the BCB Cycloctene polymer.
Keywords: gold catalysis • pentalene • polycyclic aromatic
hydrocarbons • tetrayne • organic-field-effect transistor
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a) An optical image of the film under cross-polarized light, and b) a 60 μm x 60
μm AFM image of the aligned ribbon arrays. The fast scan direction of the AFM
image is roughly perpendicular to the casting direction. c) The transfer
characteristics and the gate-source voltage dependence of the charge-carrier
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10.1002/chem.201805637
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10.1002/chem.201805637
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The gold-catalyzed annulation of tetraynes provides a useful protocol in the
synthesis of U-sahped and S-shaped bispentalenes for organic semiconductors.
The naphthalene-based S-shaped naphthalene-based bispentalene shows a one
dimensional face-to-face packing pattern in solid state and a good hole mobility.
K. Sekine, J. Schulmeister, F. Paulus, K.
P. Goetz, F. Rominger, M. Rudolph, J.
Zaumseil,* and A. Stephen K. Hashmi*
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Gold-Catalyzed Facile Synthesis and
Crystal Structures of Benzene-
/Naphthalene-based Bispentalenes as
Organic Semiconductors
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