Bithiophenesulfonamide Building Block for π-Conjugated Donor-Acceptor Semiconductors

Article abstract of DOI:10.1021/jacs.6b03498

We report here π-conjugated small molecules and polymers based on the new π-acceptor building block, bithiophenesulfonamide (BTSA). Molecular orbital computations and optical, electrochemical, and crystal structure analyses illuminate the architecture and electronic structure of the BTSA unit versus other acceptor building blocks. Field-effect transistors and photovoltaic cells demonstrate that BTSA is a promising unit for the construction of π-conjugated semiconducting materials.

Full text of DOI:10.1021/jacs.6b03498

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Communication
Bithiophenesulfonamide (BTSA) Building Block
for #-Conjugated Donor-Acceptor Semiconductors
Ferdinand S. Melkonyan, Wei Zhao, Martin Drees, Nicholas D. Eastham, Matthew J. Leonardi, Melanie R.
Butler, Zhihua Chen, Xinge Yu, Robert P. H. Chang, Mark A. Ratner, Antonio F. Facchetti, and Tobin J. Marks
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 23 May 2016
Downloaded from http://pubs.acs.org on May 23, 2016
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Bithiophenesulfonamide (BTSA) Building Block for π-
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§
#
#
§
§
Ferdinand S. Melkonyan, Wei Zhao, Martin Drees, Nicholas D. Eastham, Matthew J. Leonardi,
§
#
§
§,†
§
Melanie R. Butler, Zhihua Chen, Xinge Yu, Robert P. H Chang, Mark A. Ratner, Antonio F. Fac-
,§,#
,§,†
chetti,* Tobin J. Marks*
§
Department of Chemistry and the Materials Research Center, the Argonne Northwestern Solar Energy Research Center
ANSER), and Department of Materials Science and Engineering Northwestern University, 2145 Sheridan Road, Evanston,
†
(
Illinois 60208, United States
#
Polyera Corporation, 8045 Lamon Avenue, Skokie, Illinois 60077, United States
Supporting Information Placeholder
1
4
other aromatic amides and imides (Fig. 1a). Surpris-
ingly, and in contrast to the carbon analogs, employing
sulfonamide/imide acceptor functionalities in organic
semiconducting materials has been underexplored. Here
we report the design and realization of the first sulfona-
mide-based building block, bithiophenesulfonamide
ABSTRACT: We report here π-conjugated small mole-
cules and polymers based on the new π-acceptor build-
ing block, bithiophenesulfonamide (BTSA). Molecular
orbital computation, optical, electrochemical, and crystal
structure analysis illuminate the architecture and elec-
tronic structure of the BTSA unit vs. other acceptor
building blocks. Field-effect transistors and photovoltaic
cells demonstrate that the BTSA is a promising unit for
constructing π-conjugated semiconducting materials.
(BTSA). Moreover BTSA-based D-A polymers (Fig.
1
b) are synthesized and characterized, with polymers
BTSA-2T exhibiting promising OFET and OPV per-
formance characteristics.
a.
O
R
N
R
N
Organic semiconductors are one of the most important
components of new opto-electronic technologies. Due
R
N
1
O
R
N
O
O
O
O
to their low fabrication cost by solution processing, tun-
able optical and charge transport properties, and compat-
ibility with mechanically flexible plastic substrates, they
are finding application in organic light-emitting diode
O
O
N
R
N
R
S
O
N
R
O
NDI
DPP
IID
TPD
2
3
(
OLED) displays, photovoltaics (OPVs), field-effect
4
5
b.
OTMS
transistors (OFETs), and circuitry. Note that π-
conjugated in-chain donor-acceptor (D-A) polymers are
an enabling class of materials for many of these func-
R =
O
S
C
11
H
23
Si OTMS
CH3
R
S
6
O
N
P1
P2
S
C H
8
17
C
12
H
C
H
6
25
14
29
S
S
tions, and selection of appropriate D and A building
n
C
8
H
17
C
H
C
H
10
21
14
29
blocks and conjugation along the polymer backbone
governs key polymer properties such as frontier molecu-
BTSA-2T (P1-P5)
P3
P4
P5
lar orbital energies (EHOMO, ELUMO), band gap (E
g
), and
Figure 1. a. Imide-based in-chain acceptors widely used for con-
structing organic semiconductors; b. BTSA-based D-A polymers.
local dipole moments affecting intermolecular interac-
7
tions, solid state packing, and exciton dynamics. Final-
Earlier this Laboratory developed a bithiopheneimide
(BTI) acceptor unit, which enabled high performance
ly, existing efficient cross-coupling synthetic methodol-
1
0c
8
ogies facilitate access to libraries of new polymers by
p- and n-type OFET polymers (mobility > 0.1-1.0
simply combining known units with newly developed
2
15
9
cm /Vs) as well as a highly efficient donors for BHJ
OPVs with power conversion efficiencies (PCEs) near
building blocks. Thus, new materials advances rely
heavily on discovering novel elementary building
1
6
10
9%. Thus, with BTI as the starting unit we envisioned
incorporating a dipolar SO group (Fig. 2, Fig. S1). Ac-
blocks.
2
Historically, oligothiophenes and related heterocycles
dominated the organic semiconductors field as weak
cording to DFT computations, SulfoBTI structures ex-
hibit relatively large dihedral angles (~30º) between the
thiophene rings whereas the BTSA unit is far more pla-
nar (14º). In addition, the 6-membered BTSA ring is
inherently less sterically congested than the 7–
11
donor (D) or π-bridging units. Acceptor units (A) in-
12
clude electron-poor heterocycles (benzofused azoles),
heterocycles with electron-withdrawing groups, and
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Page 2 of 5
membered SulfoBTI core. Furthermore, recent work of
Yu et al indicates that strong electron-withdrawing func-
tionalities connected to another EWG may create traps
yields). Mitsunobu alkylation was used to introduce a
secondary alkyl chain (4c). Recently, Bao reported
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using siloxy-terminated chain to modify intermolecular
interactions in isoindigo-based polymers to enhance
17
and decrease charge transport efficiency. Thus, on the
21
basis of the abovementioned steric and electronic con-
siderations, the BTSA unit was selected as the synthetic
target.
OFET performance. In the BTSA system, siloxy-
terminated alkyl substituents are readily introduced (4b).
Prior to polymer synthesis, a BTSA small molecule
(SM) that models the target polymer backbone was pre-
pared and characterized by single-crystal X-ray diffrac-
tion (Fig. 3, Scheme S7). The BTSA core architecture is
in good accord with the DFT result, having a nearly pla-
nar core and a dihedral angle of 12.2º between the thio-
phene rings. Interestingly, the bithiophene moiety on the
R
R
N
O
O
O
N
O
O
R
O
S
O
N
S
O
S
S
O
R
N
O
O
0
1
2
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0
S
S
S
S
S
S
S
S
BTI
2
SO side of the molecule is twisted by 13.2º relative to
monoSulfoBTI 30º
SulfoBTI
30º
BTSA
14º
the corresponding core thiophene with a syn-like thio-
phene conformation. The bithiophene moiety joined to
the core N-side is far less twisted (3.7º) and has an anti-
like conformation. SM has a short 3.49 Å π-π stacking
distance between bithiophene planes, and the key BTSA
Figure 2. BTI-based design of sulfonamide-based building blocks
and DFT models (B3LYP/6-31G**)
The optimized synthesis of unsubstituted BTSA (1) is an
efficient 3-step procedure (Scheme 1). Installing the thi-
ophene-3-sulfonyl group in N-Boc-3-aminothiophene
affords sulfonamide 2 in high yield, which then under-
goes the key anionic oxidative cyclization to produce 3.
Ultimately, protecting group removal yields bithio-
phenesulfonamide 1. The high overall yield, simplicity
of this 3-step sequence, and possibilities for BTSA
scale-up represent one of the most concise and efficient
building block syntheses to date for organic semicon-
2
sulfonamide SO N functionality has 7 short intermolec-
ular S=O∙∙∙H-C contacts, portending strong and unique
22
intermolecular packing characteristics.
1
8
ductors. Next, the BTSA core was functionalized with
selected solubilizing alkyl and halogen
Scheme 1. Synthesis and Functionalization of BTSA
1
. BuLi (2.2 equiv)
Boc
NH
Boc
O
Boc
O
O
O
O
2. CuCl (4 equiv)
THF, -78 oC-rt, 12 h
2
O
S
N
S
N
S
Cl
NaH (1.1 equiv)
THF, 0 oC-rt, 6 h
S
S
S
S
S
S
via
2
, 90%
S
S
3, 65%
Li Li
O
O
HN
S
TFA (10 equiv)
DCM, reflux, 3 h
S
S
1, 85%
i, ii
ii, i
Figure 3. Molecular structure and packing of model acceptor SM.
i, ii,iii
iv, i
OTMS
C
7
H
15
S
Next, in-chain D-A polymers were synthesized using
bithiophene as the D block to initially assess macromo-
lecular properties. All new polymers were prepared via
R2
O
H
3
C
O
C
7
H
15
O
O
O
Si
O
C
11
H
23
O
O
N
S
TMSO
6
N
S
N
S
R
1
N
S
Br
S
S
Br
Br
S
S
Br Br
S
Br
Br
S
S
Br
23
Stille cross-coupling (Scheme 1, Tables S1, S2), and
Table 1 collects relevant chemical and physical proper-
ties. P1 and P2 are marginally soluble while polymers
with secondary chain (P3) and long α-branched (P4)
4da, 62%, R1 = C12
R2 = C10
H
25
21
4
a, 77%
4b, 27%
4c, 41%
H
4
db, 53%, R1 = R2 = C14
H
29
Overall yields of monomers 4 from BTSA (1). (i) Br
DCM/AcOH (4a-b) or DCM (4c, 4da, 4db), rt, 8 h; (ii) K CO
AlkBr (1.5 equiv), DMF, 80 ºC, 12h; (iii) Karstedt catalyst (0.5 mol%),
(TMSO) MeSiH (1.5 equiv), toluene, 80 ºC, 12 h; (iv) DIAD (1.5 equiv),
PPh (1.5 equiv), heptadecan-9-ol (1.1 equiv), THF, 0 ºC-rt, 36 h
2
(2.5 equiv),
2
3
(1 equiv),
substituents are more soluble, and GPC reveals M
and 11.5 KDa, respectively. P5 with the longest alkyl
chain exhibits the best solubility and the highest M in
the series (14.3 kDa). HOMO/LUMO energies and E
= 6.3
n
2
3
n
g
1
9
substituents (Scheme 1). Note that the sulfonamide
group’s strong electron-withdrawing character not only
imbues the BTSA unit with favorable FMO energies but
also provides sufficient acidity for incorporating alkyl
were estimated by cyclic voltammetry (CV) and optical
absorption spectroscopy. P1 and P2 have identical solu-
g
tion phase E values (~1.85 eV) whereas those of P3–P5
are slightly larger (Table 1) likely because the longer
24
chains using a weak base (K
4a-b) and α-branched (4da, 4db) primary alkyl substit-
uents were introduced via simple alkylation (30-80%
2 3
CO ). Thus, both linear
alkyl chains attenuate polymer aggregation. The solid-
(
state E
g
s are similar to those in solution, suggesting sim-
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5.5% was measured for the device with “inverted” archi-
ilar degrees of aggregation (Figs. S6-S10). For all poly-
1
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3
4
5
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9
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1
1
1
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2
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5
5
5
6
mers, the CV experiments reveal distinct quasireversible
oxidation and irreversible reduction processes (Table 1,
Fig. S11-S15). Thus, EHOMO and ELUMO were estimated
tecture (Fig. 4C). The high Voc (0.85 V) and FF (68.2%)
can be attributed to good HOMO energetic positioning
and the pronounced P5 crystallinity, respectively. TEM
and AFM images of the P5:PC71BM blend were taken to
probe OPV internal morphology (Fig. 4D), and clearly
reveal polymer:fullerene nanoscale phase separation
with 30-50 nm domains. Such phase segregation pro-
motes bicontinuous network formation, hence facilitates
from the oxidation onset and E
ranges, 5.2-5.4 and 3.4-3.5 eV, respectively. TGA and
DSC indicate appreciable thermal stability with T > 300
g
, and fall within similar
d
ºC, and no obvious thermal transitions (Figs. S16-S19).
Table 1. Polymers P1-P5 Physical Properties*
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(A)
(C)
opt
M
n
/PDI
E
g
, Sol/Film
1.85/1.83
1.84/1.83
1.90/1.89
1.89/1.86
1.89/1.84
E
HOMO
E
LUMO
µ
h
P1
P2
P3
P4
P5
3.3/1.51
-
-5.24
-5.21
-5.30
-5.34
-5.39
-3.41
-3.38
-3.41
-3.48
-3.55
-
-
-4
6.3/1.7
11.5/2.6
14.4 4.6
4.4*10
0.02
0.06
2
*
n h
M , E, and µ given in kDa, eV, and cm /Vs, respectively; EHOMO deter-
(B)
(D)
g h
mined as onset of CV oxidation potential; ELUMO = EHOMO + E (Film); µ
P5:PC BM
7
1
measured in saturation regime.
To characterize polymer charge transport properties,
bottom gate top contact (BGTC) OFETs of structure
Si/SiO (300nm)/OTS/Polymer/Au(35nm) were fabricat-
2
ed. Considering the poor solubility and film quality of
P1 and P2, only P3–P5 were investigated. The BTSA-
2
T polymers exhibit OFET response with distinct p-type
charge transport. All OFETs have high on/off current
Figure 4. (A) Transfer plot for a BGTC OTFT using P5; (B) θ-2θ
thin-film XRD patterns; (C) Illuminated and dark J-V response of
ratios and close to optimal turn-on voltages (Von; Table
-
4
S4). P3 exhibits modest hole mobility, µ
h
= 4.4 x 10
an (ITO/ZnO/P5:PC71BM/MoO
3
/Ag) inverted architecture OPV
2
cm /Vs, whereas that of P4 is significantly greater,
.022 cm /Vs. Importantly, BGTC transistors fabricated
device; (D) AFM height and TEM (inset) images of P5:PC BM
7
1
2
0
(1:2 ratio) blend.
using P5 as a semiconductor layer exhibit µ = 0.06
h
2
5
charge extraction and enhances the FF. The blend film
AFM image shows the same nanoscale phase separation
with surface features on a similar size scale extending in
a continuous network across the film. These networks
lessen the grain boundary densities and facilitate carrier
migration. The AFM and XRD data for a pristine P5
film and one blended with PC71BM clearly indicate that
P5 retains its crystallinity and “edge-on” orientation
after fullerene blending (Figs. S30-S32). The OPV per-
formance of BTSA-based materials can doubtless be
further enhanced by the optimizing the donor monomer,
cm /Vs, current modulation Ion/Ioff = 10 , and threshold
voltage Vth = -9 V (Fig 4A; details in Figs. S24-S27,
h
Table S4). Interestingly, µ in the TGBC architecture is
slightly smaller. Although these transport data are not
groundbreaking, they suggest that the BTSA class in-
cludes promising semiconductors.
2θ XRD and AFM were used to probe film morphology
25
and to understand P3–P5 performance difference. In-
terestingly, the carrier mobilities of these polymers cor-
relate with the XRD-derived film crystallinity. Thus, the
highest mobility P5 exhibits the strongest Bragg reflec-
tions, and large, extended domains as observed by AFM
27
solubilizing substituents, and processing conditions.
In summary, a conceptually new building block for or-
ganic semiconductors was designed and realized. Built
on the previously unexplored BTSA unit, BTSA-2T
polymers demonstrate promising preliminary results as
p-type OFET materials and donor materials for OPVs.
We believe that future development of BTSA and other
sulfonamide materials is appealing and can advance the
organic semiconducting materials field.
(
Fig. 4B, Fig. S23). The secondary alkyl chains in P3
enhance solubility and favor uniform film formation,
however strongly reduce polymer backbone interactions
and crystallinity. Note that P4 film crystallinity and hole
mobility lie between those of P3 and P5. Furthermore,
the first Bragg reflection position corresponds to lamel-
lar “edge-on” packing, having d-spacings of 15.6 Å,
1
9.9 Å, and 22.4 Å for P3–P5, respectively, in agree-
ment with the estimated N-chain lengths (Figs. S20-23,
26
Table S3).
ASSOCIATED CONTENT
Finally, BHJ OPVs were fabricated with P5 as the donor
semiconductor in both conventional and inverted archi-
tectures (Figs. S28, S29, Table S5). The highest PCE =
Supporting information.
Experimental details and characterization data and images.
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AUTHOR INFORMATION
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(
Corresponding Author
a-facchetti@northwestern.edu (A.F.);
t-marks@northwestern.edu (T.J.M.).
2
Notes:
No competing financial interests have been declared.
(13) Liang, Y.; Feng, D.; Wu, Y.; Tsai, S.-T.; Li, G.; Ray, C.; Yu, L.
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J. Am. Chem. Soc. 2009, 131, 7792.
(14) (a) Guo, X.; Facchetti, A.; Marks, T. J. Chem. Rev. 2014, 114,
ACKNOWLEDGMENT
8
943; (b) Stalder, R.; Mei, J.; Graham, K. R.; Estrada, L. A.;
Reynolds, J. R. Chem. Mater. 2014, 26, 664.
15) (a) Guo, X. G.; Ortiz, R. P.; Zheng, Y.; Hu, Y.; Noh, Y. Y.;
Baeg, K. J.; Facchetti, A.; Marks, T. J. J. Am. Chem. Soc. 2011, 133,
405; (b) Guo, X. G.; Zhou, N. J.; Lou, S. J.; Hennek, J. W.; Ortiz, R.
This research was supported in part by award
70NANB14H012 from U.S. Department of Commerce, Na-
tional Institute of Standards and Technology as part of the
Center for Hierarchical Materials Design (CHiMaD; F.S.M),
the Argonne-Northwestern Solar Energy Research Center
(
1
P.; Butler, M. R.; Boudreault, P. L. T.; Strzalka, J.; Morin, P. O.;
Leclerc, M.; Navarrete, J. T. L.; Ratner, M. A.; Chen, L. X.; Chang,
R. P. H.; Facchetti, A.; Marks, T. J. J. Am. Chem. Soc. 2012, 134,
18427.
(
ANSER; N.D.E.; M.J.L.), an Energy Frontier Research Cen-
ter funded by the U.S. DOE, Office of Science, Office of
Basic Energy Sciences under Award Number DE-SC0001059,
and the Northwestern U. Materials Research Science and En-
gineering Center under NSF grant DMR-1121262 (X.Y. ,
M.S.B.). M.S.B. was an NSF Predoctoral Fellow and M.J.L.
an NDSEG Fellow.
(
16) (a) Zhou, N. J.; Guo, X. G.; Ortiz, R. P.; Li, S. Q.; Zhang, S. M.;
Chang, R. P. H.; Facchetti, A.; Marks, T. J. Adv. Mater. 2012, 24,
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Table of Contents Graphic
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BTSA building block for OFET and OPV materials
gram scale
Boc
NH
O
O
O
O
3 steps
HN
S
S
Cl
S
N
S
S
S
50% Overall yield
Unprecedented Sulfonamide
Voc = 0.85
Jsc = 9.5
FF = 68.2
O
0
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η = 5.5%
O
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n
BTSA-2T
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ACS Paragon Plus Environment