Synthesis, Structures, and Properties of BN-Dinaphthothiophenes: Influence of B and N Placement on Photophysical Properties and Aromaticity

Article abstract of DOI:10.1021/acs.joc.0c00541

Substitution of the Ca? C functionality with the isosteric and isoelectronic B-N moiety has emerged as a powerful way to expand the family of polycyclic aromatic hydrocarbons. In this paper, two types of BN-dinaphthothiophene (BN-DNT) derivatives with dif

Full text of DOI:10.1021/acs.joc.0c00541

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Article
Synthesis, structures, and properties of BN-dinaphthothiophenes: influence
of the B and N placement on photophysical properties and aromaticity.
Qian Zhang, Zhe Sun, Lei Zhang, Mengyuan Li, Lingjian
Zi, Zongyu Liu, Bin Zhen, Wenfang Sun, and Xuguang Liu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c00541 • Publication Date (Web): 15 May 2020
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Synthesis, structures, and properties of BN-dinaphthothiophenes:
influence of the B and N placement on photophysical properties and
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aromaticity.
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Qian Zhang,a Zhe Sun,a Lei Zhang,c Mengyuan Li,a Lingjian Zi,a Zongyu Liu,a Bin Zhen,a Wenfang Sun,d
Xuguang Liu*a,b
a.Tianjin Key Laboratory of Organic Solar Cells and Photochemical Conversion, Tianjin Key Laboratory of
Drug Targeting and Bioimaging, School of Chemistry and Chemical Engineering, Tianjin University of
Technology, Tianjin 300384, People’s Republic of China.
Email: xuguangliu@tjut.edu.cn
b.Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People’s
Republic of China.
c.School of Science, Tianjin Chengjian University, Tianjin 300384, People’s Republic of China.
d.Department of Chemistry and Biochemistry, North Dakota State University, Fargo, North Dakota 58108-
6050, United States
ABSTRACT: Substitution of the C=C functionality with the isosteric and isoelectronic B-N moiety has
emerged as a powerful way to expand the family of PAHs. In this paper, two types of BN-
dinaphthothiophene (BN-DNT) derivatives with different B and N substitution patterns were synthesized
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in short steps from commercially available materials. X-ray crystallographic analysis revealed that BN-
DNT 1 and 2 had rigid and planar frameworks. Their photophysical properties and the aromaticity of the
BN rings of the BN-DNTs were slightly dependent on the B and N substitution pattern. However, their
response towards fluoride anions was greatly dependent on the B and N substitution pattern.
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INTRODUCTION
Because of their unique properties, polycyclic aromatic hydrocarbons (PAHs) are of immense interest
in various areas of organic chemistry, medicinal chemistry, and materials chemistry. Doping with
heteroatoms has emerged as an effective way to tune the properties of PAHs.1 Boron (B) and nitrogen
(N) co-doped PAHs, in which a C=C unit is replaced with an isoelectronic BN unit, were actively
explored at the beginning of 21st century. This strategy is an efficient way to create new BN aromatics
with fruitful electronic properties. 2 Although many BN-perturbed analogs of PAHs now exist,2,3 the
consequences of the BN/C=C replacement on the electronic structures and photophysical of typical
PAHs still need to be explored. In BN arenes with more than one BN unit, one fundamental question
is the effect of the relative BN position on the chemical and photophysical properties. However,
investigations on this have been limited,4 presumably because of the great challenges associated with
precisely controlling the relative BN position in the same conjugated scaffold.
Among the various PAHs, five-ring picene, which is an armchair-structured isomer of pentacene, has
attracted attention as an active layer in organic field-effect transistors.5 Replacement of the central
benzene ring of picene with thiophene produces dinaphthothiophene (DNT, Figure 1).6 Since their first
synthesis in 1960,7 DNTs have attracted great interest both for synthetic methods and in materials
science.6 Although BN picene-type molecules have been reported3e, BN analogs of DNT have been
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underexplored. Prompted by our continued interest in the development of novel BN-arenes,3d,3e in this
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work, we focused on the synthesis and properties of two types of BN- dinaphthothiophenes (BN-
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DNTs),
1 and 2 (Figure 1). Two B atoms are directly connected to the central thiophene ring and two
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N atoms are connected to the terminal benzene ring in BN-DNT 1, and the B and N placement in
isomer BN-DNT 2 is switched (Figure 1). We systematically investigated the solid-state structures
and photophysical properties of BN-DNTs 1 and 2, and how the B/N orientation affected their
properties.
Figure 1. Molecular structures of picene, DNT, and BN-DNTs 1 and 2.
RESULTS AND DISCUSSION
The synthetic route to BN-DNT 1 is illustrated in Scheme 1. Two-fold Suzuki cross-coupling of 2,5-
dibromothiophene
3 to two equivalents of (2-aminophenyl)boronic acid furnished 2,2'-(thiophene-2,5-
diyl)dianiline 4a,8 which could be alkylated to give 2,2'-(thiophene-2,5-diyl)bis(N-hexylaniline) 4b
.
Nitrogen-directed borylation of 4a or 4b with dichlorophenylborane (PhBCl2) proceeded smoothly to
give BN-DNT 1a or 1b, respectively, in moderate yield. Unlike the dual Friedel–Crafts-type
electrophilic borylation reaction on the central benzene, which was unsuccessful without the help of a
trimethysilyl (TMS) group,4b the two-fold borylation of
4 was successful presumably because of the
more electron-rich nature of the central thiophene ring. We were able to obtain the X-ray structure of
BN-DNT 1a, which unambiguously confirmed the formation of 1.
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Scheme 1. Synthetic route to BN-DNTs 1a and 1b.
The skeleton of the other isomer BN-DNT 2 was synthesized in a stepwise manner (Scheme 2). Double
Suzuki cross-coupling of 2,5-dibromo-3,4-dinitrothiophene
5 with two equivalents of phenylboronic
acid generated 3,4-dinitro-2,5-diphenylthiophene
6. Hydrogenation of nitro groups in 6 produced 2,5-
diphenylthiophene-3,4-diamine
group,10 heating the diamine
7
in high yield.9 Following the procedure reported by Perepicha’s
7
with excess PhBCl2 generated BN-DNT 2a in low yield even at high
temperature, presumably because of the less electron-rich character of the benzene ring.10 We expected
that the acidity of N-H protons could be problematic for further application. Next, we tackled the
synthesis of 2b, in which an ethylene bridge fit well between the two N atoms. Condensation of
diamine
7
with oxalaldehyde produced 5,7-diphenylthieno[3,4-b]pyrazine
8. Subsequent
hydrogenation of
8 using Pd/C under hydrogen yielded tetrahydropyrazine 9. It should be noted that 9
must be isolated and purified rapidly and stored under an inert atmosphere because it can be re-
oxidized back to 8 if exposed to air for a long time. Finally, borylation of 9 with excess PhBCl2 yielded
BN-DNT 2b with a low yield (Scheme 2). It should be noted that mono-borylated by-products were
observed in both cases, which are difficult to be isolated and purified. In addition, we also observed
small amount of unsolvable by-product in the final borylation step of synthesis of BN-DNT 2a and 2b
.
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Scheme 2. Synthetic route to BN-DNTs 2a and 2b.
All the BN-DNTs and their corresponding precursors were fully characterized. The 11B NMR of BN-
DNTs 1 and
2
displayed broad peaks at 35.0–37.4 ppm, which were indicative of sp2 hybridized
character of boron atom. BN-DNTs 1a and 2b were further characterized by single-crystal X-ray
diffraction (Figure 2, selected bond lengths are highlighted).11 The two molecules were almost planar
and the angle between the two terminal benzene rings of the main scaffold was 7.0° (1a, twisting) or
13.3° (2b, bending). The phenyl group attached on the B atom was twisted and deviated from the main
backbone by 46–64°, which limited conjugation. Due to poor quality of the X-ray structure of 2b, only
the bond lengths of 1a are discussed here. The B-N bonds lengths of 1a are between the length of a
typical B-N single bond (1.58 Å) and B=N double bond (1.403 Å). This is indicative of the BN having
double-bond character. Moreover, shorter B-C bond lengths (1.536–1.566 Å) were also observed in
the BN ring, and are consistent with other reports on BN arenes.3 The crystal packing diagrams for
BN-DNT 1a and 2b are shown in Figure S1 in the Supporting Information. BN-DNT 1a displays
slipped π-stacks. In the stack, the interplanar distances between the two layer is around 3.6 Å. In
contrast, BN-DNT 2b adopts a herringbone packing pattern, which is quite different with its analogues
(the terminal two benzene rings are replaced by two thienyl rings) reported by Perepichka’s group. [10]
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The angles between the two slipped stacked columns is around 62o in packing diagram of 2b. These
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results demonstrated that BN substitution pattern can affect their solid-state structures.
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Figure 2. Solid-state structures of BN-DNTs 1a and 2b with views parallel and perpendicular to the
polycyclic planes. Ellipsoids contour are set at the 50% probability level. H-atoms have been omitted
for clarity. a The quality of the structure of BN-DNTs 2b is poor.
To understand the effects of BN substitution and the orientation patterns of BN units on the aromaticity
of the BN-DNT, we performed nucleus-independent chemical shift (NICS) computations (Figure 3
and Figure S2).12 DNT displayed high aromaticity for each ring. However, both BN-DNTs 1a and 2b
showed moderate aromatic features for the BN ring (1a, −4.57 ppm; 2b, −4.26 ppm). The NICS (1)
values of BN-DNT 1b (−4.35 ppm) and 2a (−4.09 ppm) are shown in supporting information (Figure
S2). The NICS (1) value of BN ring in BN-DNT 1 was more negative than that in BN-DNT 2, which
indicates BN-DNT 1 has slightly stronger aromaticity. This is also supported by the shorter B-N bond
lengths observed in BN-DNT 1a (Figure 2).
Figure 3. NICS (1) values (in ppm) of BN-DNT 1a, 2b and DNT.
We recorded UV-Vis absorption and emission spectra of BN-DNT 1a and 2b (Figure 4) and BN-DNT
1b and 2a (supporting information, Figure S4), and obtained their absorption and emission band
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maxima (Table 1). The UV-Vis absorption spectra of 1a and 2b showed vibronically split bands, which
suggests they have structural rigidity. The absorption band below 400 nm could be assigned to the π-
π* transitions of the aromatic core, which was also consistent with their minor solvent effect (Figure
S5). The optical band gaps of 1a (3.23 eV) and 2b (3.16 eV) deduced from the absorption onset were
somewhat smaller than the calculated HOMO–LUMO gaps in the gas phase (1a, 3.92 eV; 2b, 3.81
eV) (Figure 5). BN-DNT 2b showed a slightly red-shifted absorption band compared with 1a. The
alkyl chain on the N atom of BN-DNT had a negligible effect on the absorption and emission spectra
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(Figures 4 and S4). BN-DNTs 1 and
2 exhibited blue emission in CH2Cl2 (360–475 nm) (Figure 4: 1a
and 2b; Figure S4: 1b and 2a). Again, BN-DNT 2b showed a slightly red-shifted emission band
compared with 1a. Furthermore, the alkyl chain on the N atom had almost no effect on the emission
energies of BN-DNTs 1 and 2, but it did affect the quantum yield (1a 0.11, 1b 0.32; 2a 0.11, 2b 0.05).
Small Stokes shifts of BN-DNTs 1 and
2 were also observed (Figures 4 and S4, Table 1). Compared
with its analogues (the central thiophene rings is replaced by a benzene ring) reported by our group
earlier[3e], both of the absorption and emission energy of BN-DNT 2b changed slightly. Similarly,
compared with other analogues of BN-DNT 2b (the terminal two benzene rings are replaced by two
thienyl rings; λabs = 397 nm, λem = 410 nm) reported by Perepichka’s group [10], the absorption spectra
shifted around 5 nm and emission spectra blue shifted approximately 13 nm. In addition, both of the
absorption and emission spectra of BN-DNT 1a changed a little compared to the anti-type molecule
(the central thiophene rings is replaced by a benzene ring; λabs = 371 nm, λem = 380 nm, 399 nm)
reported by Zhang’s group. [4b]
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Figure 4. The normalized absorption (left) and emission spectra (right) of 1a and 2b in CH2Cl2 at a
concentration of 10−5 M.
Table 1. Photophysical properties of BN-DNTs 1a, 1b, 2a and 2b in CH2Cl2.
opt
comp λabs
λonset
nm
λem
Φpl
Stokes shift EG
nm
nm
(102 cm-1)a
8.77
(eV)b
348, 364
384
384
386
392
376, 394
380,397
382,397
379, 397
0.11
0.32
0.11
0.05
3.23
3.23
3.21
3.16
1a
1b
2a
2b
347,363
349,368
351, 370
12.3
9.96
6.42
a Stokes shift = 1/λabs-1/λem. b Optical band gap EGopt = 1240/λonset
To gain an in-depth understanding of the electronic properties of BN-DNT compared with DNT, we
performed density functional theory calculations at the B3LYP/6-311+G(2d,p) level. Plots of the
HOMO and LUMO energy levels are shown in Figure 5 (1a and 2b) and Figure S3 (1b and 2a). Both
the HOMO and LUMO of BN-DNT 1 and BN-DNT 2 were delocalized on the central BN-DNT
backbone, and had negligible contributions from the phenyl group attached to B. The BN replacement
had a negligible effect on the LUMO energy level (1a, −1.78 eV; 1b, −1.69 eV; 2a, 1.71 eV; 2b, −1.68
eV), but increased the HOMO level (1a, −5.70 eV; 1b, −5.63 eV; 2a, −5.55 eV; 2b, −5.49 eV) of BN-
DNT compared with DNT (LUMO, −1.71 eV; HOMO, −5.90 eV). Consequently, BN-DNT had a
smaller bandgap (1a, 3.92 eV; 1b, −3.94; 2a, 3.84 eV; 2b, 3.81 eV) than DNT (4.19 eV).
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Figure 5. Calculated molecular orbitals of BN-DNT 1a, 2b and DNT.
Organoboron compounds are widely used as sensors for environmentally harmful fluoride ions.13
Obvious optical changes in both absorption and emission spectra were observed on addition of
tetrabutylammonium fluoride (TBAF) to a solution of BN-DNT (Figure 6 and Figure S6). Addition
of TBAF to BN-DNT 1a produced a new absorption band at around 425 nm, and the intensity of the
original absorption band decreased (Figure S6). Fluoride addition to 1a led to the appearance of a new
emission band at around 525 nm and the intensity of the original emission band decreased (Figure 6).
BN-DNT 1b displayed similar phenomena on addition of TBAF (Figure S6). Upon addition of TBAF
to the solution of 2b, the intensity of the original absorption band decreased and a new band appeared
Figure 6. Changes in emission spectra of 1a (λex = 300 nm) and 2b (λex = 300 nm) in tetrahydrofuran
upon addition of TBAF.
at around 430 nm. By contrast, the fluorescence intensity of BN-DNT 2b decreased dramatically with
generation an extremely weak new band around 510 nm (Figure 6). BN-DNT 2a showed a similar
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response to TBAF as 2b (Figure S6). The binding constants were determined to be 3.3 ×105 M-1 (1a),
1.8 ×106 M-1 (1b), 5.7 ×105 M-1 (2a), 1.5 ×106 M-1 (2b). In order to gain further insight into the binding
properties, we treated the 1-F or 2-F adduct with a stronger fluoride scavenger such as BF3·OEt.3c We
found that the the 1a-F and 1b-F can be converted back to the starting material 1a/1b by treatment with
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.
BF3 OEt. On the other hand, the 2a-F and 2b-F can be partially converted back to the starting material 2a/2b
.
by treatment with BF3 OEt (See Figure S7 in the Supporting Information)
.
The observed absorption
spectra change can be also predicted by DFT calculations, details can be found in the Supporting
Information (Figure S3 and Table S4).
We also monitored fluoride addition to BN-DNT using 11B NMR and found that the 11B NMR signal
moved from 35.0–37.4 ppm to 2.0–4.6 ppm (Figures S8–S11), which is characteristic of
tetracoordinated boron. Most of the reported organoboron compounds cause blue-shifts of the
absorption spectra and quenching of the original fluorescence upon addition of fluoride ions.13
Relatively fewer examples of spectral red-shifts have been documented.4e,4f,10 The distinguishable
behaviors of BN-DNT 1 and
2 towards fluoride ions indicate the high importance of precise control
of BN substitution patterns in BN aromatics.
Picene-type molecules typically show good field-effect mobilities.5 We measured the hole mobilities
of BN-DNT 1a and 2a using the space-charge-limited current method (Figure S12).14 The hole
mobilities of BN-DNT 1b and 2b were not measured because of their poor film-forming properties.
The
fabricated
device
structure
was
fluorine-doped
tin
oxide/poly(3,4-
ethylenedioxythiophene):poly(styrene sulfonate)/BN-DNT/Au. The hole mobility data were extracted
by fitting J–V curves (Figure S12). The hole mobility of BN-DNT 1a was 1.539 × 10−3 cm−2·V−1·S−1
and around three times that of BN-DNT 2a (0.538 × 10−3 cm−2·V−1·S−1).
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CONCLUSIONS
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In conclusions, we have synthesized two BN-DNTs with relatively different BN position in short steps.
Experimental results and DFT calculations revealed that the BN orientation slightly impacted the
aromaticity and electronic structure. However, their responses to fluoride ion addition were greatly
dependent on the BN orientation. Therefore, precise control of the BN orientation is important in BN-
containing conjugated molecules. These finding will shed light on the future design of BN-aromatics
with more than on BN units. In addition, because of their high stabilities and rich photophysical
properties, the BN-DNTs are promising candidates for use in organic electronic materials.
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EXPERIMENTAL SECTION
General Methods:
All oxygen-sensitive and moisture-sensitive manipulations were carried out under an inert atmosphere using
either standard Schlenk techniques or a nitrogen-filled drybox. The heat source is oil bath for reactions that
require heating.
THF and toluene were purified by sodium absorption under argon. All other chemicals and solvents were
purchased and used as received. Triethylamine (extra dry, with molecular sieves), 1-bromohexane, n-BuLi (2.5
M in hexane), 1,2-dichlorobenzene, 2,5-dibromothiophene, benzeneboronic acid, Pd(PPh3)2Cl2, Pd(PPh3)4,
palladium 10% on Carbon (wetted with ca. 55% Water) were purchased from Energy Chemical (Shanghai,
China). Glyoxal were purchased from Heowns Biochemical Technology Co., Ltd. (Tianjin, China).
Dichlorophenylborane was purchased from J&K Chemical (Beijing, China). 2-aminobenzeneboronic acid
were purchased from Allychem Co., Ltd., (Dalian, China). 2,5-dibromo-3,4-dinitro-thiophene were purchased
from Whmall Co., Ltd., (Shanghai, China). Petroleum ether, ethyl acetate, dichloromethane, ethanol and THF
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were purchased from Hengshan Chemical (Tianjin, China). Toluene, dioxane and potassium carbonate were
purchased from Tianjin Chemical Reagent Company.
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1H NMR and 13C NMR spectra were recorded on a Bruker AM-400 spectrometer. The reported chemical shifts
were against TMS. 11B spectra were recorded on a Bruker AM-400 spectrometer. The reported chemical shifts
were against BF3•Et2O. High-resolution mass spectra were obtained with a micro mass GCT-TOF mass
spectrometer. IR spectra were recorded on a Tensor 27 instrument with a Bruker OPTIK GmbH (Made in
Germany) spectrometer.
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The absorption spectra of all compounds were measured by HITACHI U-3900H spectrophotometer or Thermo
evolution 201. Fluorescence measurements were carried out with an F-7000 fluorescence spectrophotometer.
Fluorescence quantum yields were determined using the comparative method, quinine sulphate were
referenced to H2SO4 (0.5 M in H2O) (λex = 366 nm, ΦF = 0.546)..[15]
Data collections for compounds 1a and 2b were performed at 113 K on a Rigaku Saturn CCD diffractometer
using graphite-monochromated MoK radiation (λ = 0.71073 Å).
Synthetic procedures of BN-DNT 1a and 1b.
2,2'-(thiophene-2,5-diyl)dianiline (4a): 2,5-Dibromothiophene (1.00 equiv, 1.00 mmol, 242 mg), 2-
aminobenzeneboronic acid (2.3 equiv, 2.3 mmol, 336 mg) and potassium carbonate (10.00 equiv, 10 mmol,
1.38 g) were added in a 200 mL dried flask fit with a condenser under N2, Then Pd(PPh3)2Cl2 (0.2 equiv, 0.2
mmol, 140 mg) was added under N2. The reaction mixture was allowed to dissolve in dioxane/water (v/v =
4/1, 20 mL) under N2. The reaction was stirred at 100 oC for 24 hours. Then 40 mL of water was added after
the reaction mixture was cooled to room temperature. The mixture was extracted with dichloromethane three
times. The combined organic phase was dried over MgSO4. After the solvents was removed, the orange oil
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was purified by silica gel chromatography with petroleum ether/dichloromethane (v/v = 10/1) to afford title
compound 4a as colorless powder (221 mg, yield = 71%). The1H NMR of 4a is identical to the reported data.[8]
1H NMR (400 MHz, CDCl3): δ 7,32 (dd, J1 = 6.8 Hz, J2 = 3.2 Hz, 2H, Ar), 7.20 (s, 2H, Ar), 7.15 (td, J = 7.9,
7.7 and 1.5 Hz, 2H, Ar), 6.81 (td, J = 7.6, 7.5 and 1.2 Hz, 2H, Ar), 6.78 (dd, J = 8.0 and 0.9 Hz, 2H, Ar), 3.99
(s, 4H, br).
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2,2'-(thiophene-2,5-diyl)bis(N-hexylaniline) (4b): To a solution of 4a (1.00 equiv, 1.35 mmol, 360 mg) in
THF (15 ml) under N2 was added n-BuLi (2.5mol/L in hexane, 1.2 ml, 2.90 mmol, 2.1 equiv) dropwise at -78
oC. After the mixture being stirred at -78 oC for 1 hour, 1-bromohexane (4.00 equiv, 5.40 mmol, 890 mg) was
added under N2. Then, the reaction mixture was stirred at room temperature for 4 hours. After removing the
solvents under reduced pressure, the brown oil was purified by silica gel column chromatography with
petroleum ether/dichloromethane (v/v = 4/1) to afford compound 4b (210 mg, yield = 35%).
M.p. 58-59 ℃. 1H NMR (400 MHz, CDCl3): δ 7.28 (d, J = 7.3 Hz, 2H, Ar), 7.23 (t, J = 9.5 Hz, 2H, Ar), 7.16
(s, 2H, Ar), 6.68-6.76 (m, 4H, Ar), 4.52 (br, 2H, NH), 3.14 (t, J = 7.1 Hz, 4H, CH2), 1.58-1.67 (m, 4H, CH2),
1.27-1.44 (m, 12H, CH2), 0.62-1.09 (m, 6H, CH3). 13C{1H} NMR (101 MHz, CDCl3): δ 145.7, 140.9, 130.8,
129.4, 126.3, 119.5, 116.6, 110.7, 44.1, 31.5, 29.3, 26.9, 22.6, 14.0. FTIR (thin film): 3413, 3072, 2360, 1918,
1600, 1508, 1457, 1316, 925, 841, 459 cm-1. HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C28H39N2S 435.2834;
Found 435.2835.
BN-dinaphthothiophene (1a): To a solution of 4a (1.00 equiv, 1.00 mmol, 266 mg) in chlorobenzene (5 mL)
under N2 was added phenyldichloroborane (4.00 equiv, 4.00 mmol, 630 mg) and triethylamine (4.00 equiv,
4.00 mmol, 404 mg). The reaction was stirred at 100 oC for 24 hours. Then, the mixture was quenched with
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water, and extracted with ethyl acetate three times; the combined organic layer was dried over MgSO4. After
removal of the solvents, the viscous brown oil was purified by silica gel column chromatography with
petroleum ether/dichloromethane (v/v = 4/1) to afford compound 1a as white powder (180 mg, 40%).
M.p. 272-273 ℃. 1H NMR (400 MHz, CDCl3): δ 8.14 (d, J = 7.9 Hz, 2H, Ar), 7.69 (br, 2H, NH), 7.45 (t, J =
7.2 Hz , 2H, Ar), 7.26-7.34 (m, 8H, Ar), 6.98-7.03 (m, 6H, Ar). 13C{1H} NMR (100 MHz, CDCl3): δ 152.7,
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138.4, 132.4, 128.1, 127.7, 127.4, 126.0, 121.7, 121.6, 118.5. 11B NMR (124 MHz, BF3 OEt2): δ 35.0. FTIR
(thin film): 3363, 3048, 2919, 2312, 1611, 1426, 1275, 745, 695, 491 cm-1. HRMS (ESI-TOF) m/z: [M - H]+
Calcd for C28H19B2N2S 437.1684; Found 437.1660.
BN-dinaphthothiophene (1b): To a solution of 4b (1.00 equiv, 1.00 mmol, 434 mg) in dichlorobenzene (5
mL) under N2 was added phenyldichloroborane (4.00 equiv, 4.00 mmol, 630 mg) and triethylamine (4.00 equiv,
4.00 mmol, 404 mg). The reaction mixture was refluxed for 36 hours. Then, the mixture was quenched with
water, and extracted with ethyl acetate three times; the combined organic layer was dried over MgSO4. After
removal of the solvents, the viscous brown oil was purified by silica gel column chromatography with
petroleum ether/dichloromethane (v/v = 10/1) to afford compound 1b as white powder (180 mg, 30%).
M.p. 137-139 ℃. 1H NMR (400 MHz, CDCl3): δ 8.25 (d, J = 8.0 Hz, 2H, Ar), 7.65 (d, J =12.0 Hz, 2H, Ar),
7.57 (t, J = 8.0 Hz , 2H, Ar), 7.36 (t, J = 8.0 Hz , 2H, Ar), 7.22 (t, J =8.0 Hz, 2H, Ar), 7.11 (t, J =8.0 Hz, 2H,
Ar), 6.85 (d, J =8.0 Hz, 2H, Ar), 3.94-3.96 (m, 4H, CH2), 1.93-1.55 (m, 4H, CH2), 1.47-1.18 (m, 12H, CH2),
1.00-0.80 (m, 6H, CH3). 13C{1H} NMR (100 MHz, CDCl3): δ 151.6, 144.0, 142.9, 139.7, 131.5, 127.9, 127.3,
.
126.7, 125.7, 123.0, 121.1, 116.3, 47.6, 31.3, 30.6, 26.4, 22.5, 14.0. 11B NMR (124 MHz, BF3 OEt2): δ 36.4.
FTIR (thin film): 3566, 3069, 3005, 2955, 2855, 2360, 1606, 1429, 1285, 1120, 744, 679 cm-1. HRMS (ESI-
TOF) m/z: [M - H]+ Calcd for C40H43B2N2S 605.3562; Found 605.3535.
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Synthetic procedures of BN-DNT 2a and 2b.
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3,4-dinitro-2,5-diphenylthiophene (6): 2,5-Dibromo-3,4-dinitro-thiophene 5 (1.00 equiv, 5 mmol, 1.66 g),
benzeneboronic acid (2.10 equiv, 11.5 mmol, 1.48 g) and potassium carbonate (2.00 equiv, 10.0 mmol, 1.38 g)
were added in a 100 mL dried flask fit with a condenser under N2, Then Pd(PPh3)4 (0.05 equiv, 0.25 mmol,
0.30 g) was added under N2. The reaction mixture was allowed to dissolve in dioxane/water (v/v = 4/1, 40 mL)
under N2. The reaction was stirred at 100 oC for 12 hours. Then 40 mL of water was added after the reaction
mixture was cooled to room temperature. The mixture was extracted with dichloromethane three times. The
combined organic phase was dried over MgSO4. After the solvents was removed, the orange oil was purified
by silica gel chromatography with petroleum ether/dichloromethane (v/v = 2/1) to afford title compound 6 as
colorless powder (1.47 g, yield = 65%). The 1H NMR of 6 is identical to the reported data.[16]
1H NMR (400 MHz, CDCl3): δ 7.48-7.54 (m, 10H, Ar)
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2,5-diphenylthiophene-3,4-diamine (7): Pd/C (10 wt %, 2.00 equiv, 2.00 mmol, 220.0 mg) was added to 6
(1.00 equiv, 1.00 mmol, 326 mg) in ethyl acetate (5 mL). The flask was vacuumed and recharged with
hydrogen (0.1 MPa). The reaction mixture was heated at 70 oC for 16 hours. The reaction progress is monitored
by TLC. After the reaction completed, Pd/C was removed by filtration. Removal of solvent by vacuum gave
the compound 7, and it was used directly without further purification. The 1H NMR of 7 is identical to the
reported data.[16]
1H NMR (400 MHz, CDCl3): δ 7.51-7.56 (m, 4H, Ar), 7.43-7.45 (m, 4H, Ar), 7.27-7.32 (m, 2H, Ar), 3.66 (br,
4H, NH2).
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BN-dinaphthothiophene (2a): To a solution of 7 (1.00 equiv, 1.00 mmol, 266 mg) in dichlorobenzene (5 mL)
under N2 was added phenyldichloroborane (4.00 equiv, 4.00 mmol, 630 mg) and triethylamine (4.00 equiv,
4.00 mmol, 404 mg). The reaction mixture was refluxed for 36 hours. Then, the mixture was quenched with
water, and extracted with ethyl acetate three times; the combined organic layer was dried over MgSO4. After
removal of the solvents, the viscous brown oil was purified by silica gel column chromatography with
petroleum ether/dichloromethane (v/v = 4/1) to afford the compound 2a as white powder (90 mg, 20%).
M.p. 235-236 ℃. 1H NMR (400 MHz, CDCl3): δ 8.27 (d, J = 8.0 Hz, 2H, Ar), 8.01 (d, J = 8.0 Hz, 2H, Ar),
7.97 (br, 2H, NH2), 7.84- 7.82 (m, 4H, Ar), 7.74 (t, J = 7.2 Hz , 2H, Ar), 7.56- 7.49 (m, 6H, Ar), 7.44 (t, J =
7.2 Hz , 2H, Ar). 13C{1H} NMR (101 MHz, CDCl3): δ 138.4, 136.8, 133.4, 131.6, 130.2, 128.9, 128.1, 125.2,
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122.7, 121.2. 11B NMR (124 MHz, BF3 OEt2): δ 37.4. FTIR (thin film): 3252, 3051, 2917, 2849, 2308, 1602,
1540, 1484, 1264, 762. HRMS (ESI-TOF) m/z: [M - H]+ Calcd for C28H19B2N2S 437.1684; Found 437.1635.
5,7-diphenylthieno[3,4-b]pyrazine (8): Glyoxal (40 wt% aqueous solution, 1.10 equiv, 0.71 mmol, 0.13 mL)
was added to a solution of 7 (1.00 equiv, 0.63 mmol, 170 mg) in anhydrous ethanol (10 mL) under N2. Then,
sodium carbonate (4.00 equiv, 2.40 mmol, 260 mg) was added to the above reaction mixture. This resulting
mixture was stirred at 50 ℃ for 16 hours. Then, the red precipitate was collected by filtration under vacuum.
The red solid was purified by silica gel column chromatography with petroleum ether/dichloromethane (v/v =
2/1) to afford the compound 8 as red powder (190 mg, 92%).
M.p. 132-133 ℃. 1H NMR (400 MHz, CDCl3): δ 8.51 (s, 2H, Ar), 8.13 (d, J =8.0 Hz, 2H, Ar), 7.50 (t, J = 7.2
Hz , 2H, Ar), 7.37 (t, J = 7.2 Hz , 2H, Ar). 13C{1H} NMR (101 MHz, CDCl3): δ 144.1, 139.9, 132.8, 132.3,
128.9, 128.1, 128.0. FTIR (thin film): 3447, 3083, 3030, 2994, 1912, 1661, 1593, 1484, 1292, 1010, 738, 689.
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C18H13N2S 289.0800; Found 289.0812.
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5,7-diphenyl-1,2,3,4-tetrahydrothieno[3,4-b]pyrazine (9): Pd/C (10 wt %, 2.00 equiv, 2.00 mmol, 258 mg)
was added to 8 (1.00 equiv, 1.00 mmol, 290 mg) with hydrogen (4.0 MPa). The reaction mixture was heated
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at 50 C overnight. The reaction progress is monitored by TLC. After the reaction completed, Pd/C was
removed by filtration. Removal of solvent by vacuum gave the compound 9 with acceptable purity, and it was
used directly without further purification.
M.p. 75-77 oC. 1H NMR (400 MHz, CDCl3): δ 7.62 (d, J = 8.0 Hz, 4H, Ar), 7.46 (t, J = 7.2 Hz , 4H, Ar), 7.30
(t, J = 7.2 Hz, 2H, Ar), 4.37 (br, 2H, NH2), 3.45 (t, J = 7.2 Hz , 4H, CH2). 13C{1H} NMR (101 MHz, CDCl3):
δ 134.6, 132.3, 129.0, 126.8, 126.0, 112.0, 41.7. FTIR (thin film): 3364, 3054, 2956, 2854, 1668, 1525, 1437,
1030, 756, 695. HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C18H17N2S 293.1112; Found 293.1131.
BN-dinaphthothiophene (2b): To a solution of 9 (1.00 equiv, 1.00 mmol, 296 mg) in dichlorobenzene (5 mL)
under N2 was added phenyldichloroborane (4.00 equiv, 4.00 mmol, 630 mg) and triethylamine (4.00 equiv,
4.00 mmol, 404 mg). The reaction mixture was refluxed for 48 hours. Then, the mixture was quenched with
water, and extracted with ethyl acetate three times; the combined organic layer was dried over MgSO4. After
removal of the solvents, the viscous brown oil was purified by silica gel column chromatography with
petroleum ether/dichloromethane (v/v = 4/1) to afford the compound 2b as white powder (90 mg, 20%).
M.p. 221-222 oC. 1H NMR (400 MHz, CDCl3): δ 7.96 (dd, J1 = 8.0 Hz, J2 = 4.0 Hz, 4H, Ar), 7.73-7.69 (m, 2H,
Ar), 7.59 (dd, J1 = 6.0 Hz , J2 = 1.6 Hz, 4H, Ar), 7.51-7.43 (m, 6H, NH2), 7.37 (t, J1 = 15.2 Hz, J2 = 7.2 Hz, 2H,
Ar). 13C{1H} NMR (101 MHz, CDCl3): δ 137.5, 137.4, 133.2, 131.2, 130.9, 128.0, 127.7, 124.9, 122.1, 120.6,
45.9. 11B NMR (124 MHz, BF3 OEt2): δ 37.4. FTIR (thin film): 3007, 2311, 1602, 1476, 1267, 1071, 758.
.
HRMS (ESI-TOF) m/z: [M - H]+ Calcd for C30H21B2N2S 463.1841; Found 463.1835.
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ASSOCIATED CONTENT
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Supporting Information
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X-ray crystal characterization, spectroscopic data for all compounds, computational studies,
absorption and emission spectra. The supporting information is available free of charge on the ACS
Publication website at DOI: TO BE ADDED.
AUTHOR INFORMATION
Corresponding Author* E-mail: xuguangliu@tjut.edu.cn
ACKNOWLEDGMENTS
We gratefully acknowledge financial support from the Natural Science Foundation of Tianjin (Grant
No. 17JCZDJC37700 and 18JCQNJC06900), National Natural Science Foundation of China (Grant
No.21502140), Tianjin University of Technology, and Shanghai Institute of Organic Chemistry (Grant
No. K2015-10). We also thank the Training Project of Innovation Team of Colleges and Universities
in Tianjin (Grant No. TD13-5020) and the University Student Innovation Program.
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