Dye-sensitized solar cell utilizing organic dyads containing triarylene conjugates
Yuan Jay Chang
a, Tahsin J. Chow
a,b,*aDepartment of Chemistry, National Taiwan University, Taipei 106, Taiwan bInstitute of Chemistry, Academia Sinica, Taipei 115, Taiwan
a r t i c l e
i n f o
Article history:
Received 13 January 2009
Received in revised form 4 April 2009 Accepted 7 April 2009
Available online 16 April 2009 Keywords:
Dye-sensitized solar cell Photovoltaic
Triarylene Light harvesting Charge transfer
a b s t r a c t
A series of organic dipolar compounds containing a donor (D), a bridge (B), and an acceptor (A), forming a D–B–A type of dyads, were synthesized by convenient methods and were utilized successfully on dye-sensitized solar cells. The central bridges were made of three linearly connected arylene groups, i.e., phenylenes or thiophenylenes. The donor groups were aromatic amines, i.e., either a diphenylamine or a naphthylphenylamine group. The acceptor group was a cyanoacrylic acid, which can be anchored onto the surface of TiO2in a photovoltaic device. These devices performed remarkably well, with a typical quantum efficiency of 5–7%, and optimal incident photon to current conversion efficiency (IPCE) ex-ceeding 80%. The devices made with a naphthylphenylamine donor group performed slightly better than those made with a diphenylamine donor group. Compounds containing a phenylene–thiophenylene– phenylene bridge group performed better than those with other kinds of triarylene linkages. Their photochemical behaviors were analyzed by using time-dependent density functional theory (TDDFT) models with the B3LYP functional.
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
Organic dipolar compounds containing an electron donor (D) and an electron acceptor (A), separated by a bridge group (B), have found wide applications on the new generation of optoelectronic devices.1Electron transfer from D to A happens rapidly upon photo-excitation to generate a charge-separated species.2 Subsequent charge recombination may proceed within the molecule to gener-ate a charge-transfer (CT) emission in certain cases, or it may be guided to proceed through an external circuit such as the design in dye-sensitized solar cells (DSSCs). Because the efficiency of the solar cell competes with the internal charge recombination, the lifetime of the CT state becomes a major concern for designing the dyes. In previous reports, organic dyes using aryl amine as a donor and cyanoacrylic acid as an acceptor have exhibited promising results. For the donor group, a wide choice of aryl amines have been used such as coumarin,3 indoline,4 cyanine,5 mer-ocyanine,6 hemicyanine,7 porphyrin,8 etc., while most of them exhibited satisfactory performances. It has also been noticed that the structure of the bridge group played a crucial role in these devices. The function of a bridge group is twofold, i.e., acting both as a part of the light absorbing chromophore and also as a channel for transporting charges. A good bridge group should promote the
absorption of light over a wide wavelength region, yet retards the rate of internal charge recombination. Linearly connected arylenes serve both purposes quite well. The flexible dihedral angles be-tween adjacent aryl groups are twisted to a greater extend upon excitation to the CT state, while the electronic resonance is reduced and the rate of charge recombination slows down. In this report we describe our efforts in search of the best molecular structures of DSSC dyes. Triphenylamine is selected as the D group according to its outstanding performance in past literatures.9For the B group, a linkage containing three aryl moieties seems to fit well with the optimal distance between the centers of D and A. A series of compounds with a general formula as shown in Figure 1 were prepared. Indeed these dyes displayed remarkable performance while fabricated into photovoltaic devices.
2. Results and discussion
The synthetic sequences are outlined in Scheme 1. All com-pounds can be categorized in two groups, i.e., 1P and 1N, each are further divided into five types according to their triarylene linkages, i.e., PPP, PPS, PSP, PSS, and SSS, where P and S denote phenyl and thiophene groups, respectively. The syntheses are started from diarylamine, onto which the third aromatic substituent was added through Buchwald–Hartwig coupling reactions by the aid of Pd(OAc)2 to build up new C–N bonds.10 The structure of certain
products exhibited twofold symmetry, e.g., 2, 5, and 9, which can be justified by their1H and13C NMR spectra.
*Corresponding author.
E-mail address:[email protected](T.J. Chow).
Contents lists available atScienceDirect
Tetrahedron
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / t e t
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.tet.2009.04.024
Contents lists available atScienceDirect
Tetrahedron
The trithiophenylene linkage in compounds 9P and 9N was completed in a single step. A subsequent formylation was done by Vilsmeier–Haack reaction to give 10P and 10N.11For compounds 2P and 2N, an extension of the aryl chain was achieved by Suzuki coupling reactions to yield the aldehydes 3P, 3N, 4P, and 4N in 80– 90% yields.12The addition of a thiophene unit on 5P and 5N was done by Stille coupling with 2-bromothiophene to give 6P and 6N in ca. 80% yield.13A similar type of reaction was performed again to put on the third aryl groups in 7P–8N in 68–78% yields. The final step was a Knoevenagel condensation with cyanoacetic acid to convert carbaldehydes to cyanoacrylic acids.14All final products can be crystallized into deep color solids.
The absorption spectra of organic dyes in THF solution are dis-played inFigure 2. Each of these compounds exhibits a major ab-sorption band on the long wavelength edge at
l
max380–480 nm.This band exhibits a distinctive solvent shift, therefore is assigned a
p
–p
* transition mixed with significant CT character ( Supple-mentary data). Upon photo-excitation, the high-lying electron, mostly localized on the triarylamine (D) moiety, migrates to cya-noacrylic acid (A) on the other side of the molecule. The electron movement is heavily coupled with thep
-orbitals of the central triaryl linkage (B). The linkages containing more thiophene moie-ties displayed a greater bathochromic shift, e.g., SSSzPSS> PSPzPPS>PPP in both series. The high-lyingp
orbital in thio-phene is located at a higher potential level than that in a phenyl ring, therefore is delocalized more extensively than the latter. A better conjugation in the former is also supported by a more planar conformation. For example, the dihedral angle between adjacent aryl rings is nearly zero in SSS type structure, yet is significantly twisted (w36) in the PPP type as estimated by molecularmod-eling. The molar extinction coefficients (2–4104M1cm1) of all compounds are not much different from each other, yet are all higher than that of the well known ruthenium dyes (<2104M1cm1). It is also noteworthy inFigure 2that the ab-sorption intensity of 1N series compounds (dotted curves) is
consistently higher than the corresponding ones in 1P series (solid curves). This phenomenon seems to correspond well with the better performance of DSSC devices made with the former materials.
The first oxidation potentials (Eox), corresponding to the HOMO
level of dyes, were measured by cyclic voltammetry (CV) in THF (Fig. 3) and the results were summarized inTable 1. The LUMO levels of sensitizer were estimated by the values of Eox and the
0–0 band gaps, the latter were obtained at the intersection of ab-sorption and emission spectra. The band gap energies reduce along with the number of thiophene units, i.e., the band gaps arranged in the order of 1P-PPP (2.77)>1P-PSP (2.53)z1P-PPS (2.54)>1P-PSS (2.30)z1P-SSS (2.24), and 1N-PPP (2.78)>1N-PSP (2.52)z1N-PPS (2.52)>1N-PSS (2.32)>1N-SSS (2.16). The oxidation waves of both 1P-SSS and 1N-SSS exhibit two maxima, which indicate clearly that amine
p
-orbital resonates significantly with the nearby thiophenep
-orbital. The interaction pushes up the potential energy level of the amine donor, therefore lowers its oxidation potential. The es-timated LUMO levels of all dyes are sufficiently higher than the electron injection level of TiO2 (ca. 0.5 V), while their HOMOlevels are sufficiently lower than that of electrolyte pair I/I3
(ca. 0.4 V). Such electronic structures thus ensure a favorable exothermic flow of charges throughout the photo-electronic conversion.
The electronic configurations were further examined by theo-retical models implanted in Gaussian 03 program. Their molecular geometries were optimized by using B3LYP/6-31G*basis set first,
then the orbitals of both ground and excited states were computed by time-dependent density functional theory (TDDFT) with B3LYP functional. According to the optimized molecular geometry, the conformation of two adjacent thiophene rings is nearly coplanar, but the orientation of two adjacent phenyl rings is twisted to w36
due to steric hindrance (Supplementary data). As a result the electronic resonance is transmitted more efficiently through thio-phene moieties than through phenyl groups. A better resonance
N N N 1P-PSP 1P-PPS 1P-PSS N 1P-SSS N 1P-PPP N N N 1N-PSP 1N-PPS 1N-PSS N 1N-PPP N 1N-SSS CN COOH CN COOH S CN COOH S CN COOH S CN COOH S CN COOH S S CN COOH S S CN COOH S S S CN COOH S S S CN COOH
along thiophene moieties leads to a lower band gaps, yet the same effect also promotes the rate of charge recombination, which quenches the excited state. The HOMO/LUMO energy levels and band gaps of the dyes are listed inTable 1.
The electronic density distributions before and after photo-ex-citation can be illustrated better by the graphs in Figure 4. The
electron densities in the HOMOs are distributed mainly around the amine moieties (D), and those in the LUMOs around the cyanoa-crylic acid moieties (A). Photo-excitation pumps an electron from the HOMO to the LUMO, therefore shifts considerable amount of electron density from D to A. The difference of Mulliken charge density surrounding D, B, and A moieties before (S0state) and after
(S1state) photo-excitation was arranged in the order of magnitude
(Supplementary data). The degree of charge separation declines
Ph NH Ph N Ph N 2P) Ph = Phenyl (77%) N) Ph = Naphthyl (70%) 3P (90%); 3N (88%) 1P-PPP (64%); 1N-PPP (70%) 4P (88%); 4N (80%) 1P-PPS (70%); 1N-PPS (65%) Br Ph N S O O Ph N Ph N S CN COOH CN COOH (i) (ii) (ii) (iii) (iii) Ph N S O Ph N S 7P (78%); 7N (75%) 1P-PSP (61%); 1N-PSP (61%) Ph N S 8P (68%); 8N (68%) Ph N S 1P-PSS (69%); 1N-PSS (67%) Ph N S 5P (65%); 5N (65%) 6P (80%); 6N (78%) S S O CN COOH (iii) (iii) (v) (v) Ph N Br (iv) (i) Ph NH 9P (50%); 9N (47%) 10P (60%); 10N (72%) 1P-SSS (60%); 1N-SSS (55%) S S S N Ph
(i) (vi) (iii)
CN COOH CN COOH S S S N Ph O S S S N Ph Br
Scheme 1. Synthesis and structures of organic dyes. Reagents: (i) Pd(OAc)2/dppf, 4,40-dibromobiphenyl (2) or 1,4-dibromobenzene (5) or 2,5-bis(50-bromothiophen-20-yl)thiophene (9), toluene, 90C; (ii) (a) BuLi, triisopropylborate, THF, 78C; followed by HCl
(aq), (b) Pd(PPh3)4, 4-bromobenzaldehyde (3) or 5-bromothiophene-2-carbaldehyde (4), toluene, K2CO3; (iii) cyanoacetic acid, NH4OAc, AcOH, 90–100C; (iv) PdCl2(PPh3)2, 2-(tributylstannyl)thiophene, DMF, 90C; (v) BuLi, tributyltin chloride, THF, 78C; followed by PdCl2(PPh3)2, 4-bromobenzaldehyde (7) or 5-bromothiophene-2-cabaldehyde (8), DMF; (vi) (a) BuLi, THF, 78C (b) DMF.
300 400 500 600 700 0 1 2 3 4 (M -1 cm -1 x 10 4) Wavelength (nm) 1P-PPP 1P-PPS 1P-PSP 1P-PSS 1P-SSS 1N-PPP 1N-PPS 1N-PSP 1N-PSS 1N-SSS
Figure 2. Absorption spectra of organic dyes in THF, whereeis molar extinction coefficient. 0.0 0.2 0.4 0.6 0.8 1.0 5 0 -5 -10 -15 Potential (V) Current ( u A) 1N-PPP 1N-PPS 1N-PSP 1N-PSS 1N-SSS 1P-PPP 1P-PPS 1P-PSP 1P-PSS 1P-SSS Fc
along with the additional number of thiophenylene groups in the arrays, as a result of more coplanar conformation across the ring junctions. Such a phenomenon can best be demonstrated by a comparison of the HOMO and LUMO orbitals between 1P-SSS and 1P-PPP as shown inFigure 4. The orbitals delocalize over a wider range through the relay of thiophene groups in the former than they do through the phenylene linkages in the latter.
Typical DSSC devices with an effective area of 0.25 cm2were fabricated with the dyes as sensitizers, which were coated on the surface of nanocrystalline anatase TiO2. A mixture of I2(0.05 M), LiI
(0.5 M), and tert-butylpyridine (0.5 M) in acetonitrile solution was used as an electrolyte. The photovoltaic performance under a solar condition (AM 1.5) is summarized inTable 1The J–V curves of all dyes are shown inFigure 5. The current density maintains a con-stant value within a range of 11–17 mA cm2up to 0.4 V. Plots of IPCE at various wavelengths are given inFigure 6. The active photo-to-current conversion area of these dyes lies in the blue/green re-gion, as implied by their absorption spectra (Fig. 2). Nevertheless their optimal conversion ratios reach to ca. 80%, quite close to that of N719 at the same wavelengths. Generally speaking, the 1N series compounds perform relatively better than the 1P series com-pounds, that is, consistent with a higher absorptivity of 1N series compounds than that of 1P series compounds (Fig. 2). The naph-thalene substituent may also have provided a better environment for resonance around the nitrogen donor, thus stabilizing the pos-itive charge better. The larger size of naphthalene may also have an effect on increasing the steric hindrance to prevent the material from self-aggregation.
A comparison between the performances of 1P-SSS and 1P-PPP is worth mentioning. The former exhibited both a lower short-circuit current (Jsc¼10.9 mA cm2) and a lower open-circuit voltage
(Voc¼0.58 V) than the former (Jsc¼11.4 mA cm2; Voc¼0.65 V). The
overall field factor (FF) of the former (0.60) turned out slightly smaller than that of the latter (0.62), which led to a relatively lower quantum efficiency (3.75% vs 4.58%). The efficiency of DSSCs indeed depends upon a delicate balance between the degree of electronic resonance and the rate of charge recombination of an organic chromophore. Among all compounds, the best performance was found in compound 1N-PSP. A device made of this material exhibited Jsc value of 16.81 mA cm2, Vocvalue of 0.74 V, and FF
value of 0.57. The overall conversion efficiency (
h
) was estimated to be 7.08%, quite compatible to the well-known ruthenium complex N719. The incident photon to current conversion efficiency (IPCE) was higher than 80% at 450–470 nm region. Besides 1N-PSP, others like 1P-PSS,151N-PPS, and 1N-PSS also yielded quantum efficiency in the proximity of 6%.In summary, a series of dipolar compounds containing a triaryl-ene bridge were prepared by convenient methods and can be used as highly efficient dye sensors in organic solar cells. In their structures, either a diphenylamino (type 1P) or a naphthyl-phenylamino (type 1N) group was attached to a terminal of a tri-arylene bridge as an electron donor, while a cyanoacrylic acid moiety on the other end as an acceptor. The triarylene bridges consist of phenyl and/or thiophenyl groups linked together in a linear fashion. These compounds exhibited a high absorptivity in the blue/green region of solar light. The DSSC devices fabricated by using these materials as dye sensors displayed remarkable quan-tum efficiency, typically in a range of 5–7%. The optimal IPCE value reaches beyond 80%. The performance of 1N type compounds, in general, was slightly better than that of the 1P type. This can be ascribed partly to the higher absorptivity of 1N series compounds, and partly to a better resonance effect provided by a naphthalene moiety. The larger size of naphthalene group may also effectively hinder self-aggregation of the dyes on TiO2surface. The structure
of bridges is also influential. The presence of thiophenylene units in the bridge improves coplanarity, thus promotes better reso-nance delocalization. As a result the band gap is reduced, yet with an expense of increasing the tendency of aggregation. The adja-cent phenylene groups are twisted with large dihedral angle, nevertheless such a twisted conformation can retard the rate of charge recombination. A delicate balance needs to be tuned be-tween charge separation and charge recombination by modifying the molecular structures. The best performance among these compounds was found in 1N-PSP, which showed a maximal IPCE value of 82%, Jscvalue of 16.81 mA$cm2, Vocvalue of 0.74 V, and
FF value of 0.57, that correspond to an overall conversion effi-ciency of 7.08%.
3. Experimental section
3.1. General information
All reactions were carried out under a nitrogen atmosphere. Solvents were distilled freshly according to standard procedures.
1H and 13C NMR spectra were recorded on a Bruker 400 MHz
spectrometer. Absorption spectra were recorded on a Hewlett– Packard 8453 spectrofluorometer. The redox potentials were measured by using cyclic voltammetry on CHI 620 analyzer. Mass spectra were recorded on a VG70-250S mass spectrometer. Elementary analyses were performed on a Perkin–Elmer 2400 CHN analyzer. The starting materials diphenylamine, di-p-tolylamine, bis(4-methoxyphenyl)amine, N-naphthylaniline,
Table 1
Calculated (TDDFT/B3LYP) and experimental parameters for dyes 1Ns and 1Ps Dye HOMO/LUMOa(eV) Band gapa fa l
absb(nm)/(3(M1cm1)) E0–0b(eV) Eoxc(V) EHOMO/ELUMOd(V) Jsc(mA cm2) Voc(V) FF he(%)
1P-PPP 5.08/2.57 2.50 0.28 380(30,200) 2.77 0.85 5.35/2.58 11.43 0.65 0.62 4.58 1P-PPS 5.09/2.64 2.45 0.41 417(23,000) 2.54 0.86 5.36/2.82 13.86 0.65 0.57 5.14 1P-PSP 5.06/2.61 2.45 0.71 427(29,000) 2.53 0.79 5.29/2.77 15.36 0.69 0.50 5.25 1P-PSS 5.08/2.69 2.38 0.85 461(27,100) 2.30 0.79 5.29/2.99 16.26 0.66 0.58 6.17 1P-SSS 5.02/2.72 2.29 0.96 468(22,500) 2.24 0.58 5.08/2.84 10.89 0.58 0.60 3.75 1N-PPP 5.10/2.59 2.51 0.26 375(37,400) 2.78 0.83 5.33/2.55 11.24 0.68 0.60 4.60 1N-PPS 5.08/2.60 2.48 0.44 422(36,300) 2.52 0.82 5.32/2.80 14.20 0.66 0.60 5.68 1N-PSP 5.12/2.63 2.49 0.77 422(37,700) 2.52 0.82 5.32/2.80 16.81 0.74 0.57 7.08 1N-PSS 5.11/2.70 2.41 0.83 461(31,300) 2.32 0.81 5.31/2.99 14.28 0.71 0.60 6.12 1N-SSS 4.99/2.69 2.30 1.03 480(22,200) 2.16 0.53 5.03/2.87 11.88 0.58 0.54 3.74 N719 d d d d d d d 17.68 0.75 0.61 7.64
f: Oscillator strength for the lowest energy transition;3: absorption coefficient; Eox: oxidation potential; E0–0: 0–0 transition energy measured at the intersection of absorption and emission spectra; Jsc: short-circuit photocurrent density; Voc: open-circuit photovoltage; FF: fill factor;h: total power conversion efficiency.
aTDDFT/B3LYP calculated values. b In THF.
c Oxidation potential in THF (103M) containing 0.1 M (n-C
4H9)4NPF6with a scan rate of 100 mV s1. d E
HOMOwas calculated by Eoxþ4.5 V (vs NHE), and ELUMO¼EHOMOE0–0.
4,40-dibromobiphenyl, 1,4-dibromobenzene,
4-bromobenzalde-hyde, 5-bromothiophene-2-carbalde4-bromobenzalde-hyde, and tributyl(thiophen-2-yl)stannane were purchased from ACROS, Merck, Lancaster, TCI, Sigma–Aldrich, and purified before use. Chromatographic separa-tions were carried out on silica gel Merk Kieselgel si 60 (40– 63
m
m).3.2. Fabrication and characterization of DSSCs
A thin film of TiO2(16–18
m
m thick) was coated on a 0.25 cm2FTO glass substrate. It was immersed in a THF solution containing 3104M dye sensitizers for 12 h, then rinsed with anhydrous
acetonitrile and dried. Another piece of FTO with sputtering 100 nm thick Pt was used as a counter electrode. The active area was con-trolled at a dimension of 0.25 cm2by adhering 60
m
m thick polyester tape on the Pt electrode. The photocathode was placed on top of the counter electrode and was tightly clipped together to form a cell. Electrolyte was then injected into the seam between two electrodes. An acetonitrile solution containing LiI (0.5 M), I2 (0.05 M), and4-tert-butylpyridine (0.5 M) was used as the electrolyte. Devices made of a commercial dye N719 under the same condition was
Figure 4. Computed frontier orbitals of 1N-PSP, 1N-PSS, 1P-SSS, and 1P-PPP. The upper graphs are the LUMOs and the lower ones are the HOMOs.
0.0 0.2 0.4 0.6 0.8 0 2 4 6 8 10 12 14 16 18
Current Density (mA/cm
-2) Cell Voltage (V) 1P-PPP 1P-PPS 1P-PSP 1P-PSS 1P-SSS 1N-PPP 1N-PPS 1N-PSP 1N-PSS 1N-SSS N719
compared as a reference. The cell parameters were obtained under an incident light with intensity 100 mW cm-2, which was generated by a 300 W Xe lamp passing through an AM 1.5 filter. The current– voltage parameters of DSSCs were recorded by a potentiostat/gal-vanostat model CHI650B (CH Instruments, USA).
3.3. Quantum chemistry computation
The structures of dye were optimized by using B3LYP/6-31G*
hybrid functional. For the excited states, a time-dependent density functional theory (TDDFT) with the B3LYP functional was employed. All analyses were performed under Q-Chem 3.0 soft-ware. The frontier orbital plots of HOMO and LUMO were drawn by using Gaussian 03.
3.4. (E)-2-Cyano-3-(naphthylphenylaminotriphenylene)-acrylic acid (1N-PPP)
A mixture of 3N (242 mg, 0.51 mmol), cyanoacetic acid (52 mg, 0.61 mmol), and ammonium acetate (10 mg, 0.13 mmol) in acetic acid was placed in a three-necked flask under a nitrogen atmo-sphere and was stirred at 120C for 12 h. After cooling, the reaction
was quenched by adding water and then was extracted with CH2Cl2.
The organic layer was dried over anhydrous MgSO4and evaporated
under vacuum. The products were purified by silica gel column chromatograph eluted with CH2Cl2/acetic acid (19/1). The orange
solid was isolated in 70% yield (195 mg, 0.36 mmol), mp: 238– 240C. Spectroscopic data of 1N-PPP.1H NMR (DMSO-d
6):
d
8.29 (s, 1H), 8.06 (d, 2H, J¼8.4 Hz), 7.95 (d, 1H, J¼8.2 Hz), 7.81–7.86 (m, 4H), 7.73 (d, 2H, J¼8.3 Hz), 7.63 (d, 2H, J¼8.3 Hz), 7.43–7.51 (m, 4H), 7.34 (t, 1H, J¼7.6 Hz), 7.30 (d, 1H, J¼7.2 Hz), 7.17 (t, 2H, J¼7.8 Hz), 6.86– 6.95 (m, 5H).13C NMR (DMSO-d6):d
163.8, 154.0, 148.0, 147.7, 144.2, 142.8, 140.1, 137.0, 135.3, 131.8, 130.8, 129.8, 129.0, 127.7, 127.4, 127.3, 126.9, 123.8, 122.7, 122.4, 121.1, 116.7, 103.5. HRMS (m/z): 542.1992 (Mþ) (calcd for C38H26N2O2: 542.1994). 3.5. (E)-2-Cyano-3-(50-(400-(naphthylphenylamino)-biphenylene)thiophen-20-yl)acrylic acid (1N-PPS)
Compound 1N-PPS was synthesized according to the same procedure as that of 1N-PPP. Red solid of 1N-PPS were obtained in 65% yield, mp: 275–277C.1H NMR (DMSO-d 6):
d
8.36 (s, 1H), 7.94 (d, 1H, J¼8.2 Hz), 7.86 (d, 1H, J¼4.1 Hz), 7.84 (d, 1H, J¼8.4 Hz), 7.78 (d, 1H, J¼8.4 Hz), 7.67 (d, 2H, J¼8.3 Hz), 7.62 (d, 1H, J¼4.0 Hz), 7.57 (d, 2H, J¼8.4 Hz), 7.42–7.50 (m, 4H), 7.33 (t, 1H, J¼7.6 Hz), 7.27 (d, 1H, J¼7.3 Hz), 7.17 (t, 2H, J¼7.8 Hz), 6.90–6.94 (m, 3H), 6.83 (d, 2H, J¼8.6 Hz).13C NMR (DMSO-d6):d
164.2, 152.3, 148.1, 147.5, 146.1, 142.7, 141.0, 140.8, 135.3, 134.9, 131.7, 131.0, 130.9, 129.8, 129.0, 127.7, 127.3, 127.1, 127.0, 126.9, 126.7, 125.1, 123.7, 122.8, 122.5, 120.9, 117.2, 99.9. HRMS (m/z): 548.1555 (Mþ) (calcd for C36H24N2O2S: 548.1158). 3.6. (E)-2-Cyano-3-(p-(50-(p-(naphthylphenylamino)-phenyl)thiophen-20-yl)phenyl)acrylic acid (1N-PSP)
Compound 1N-PSP was synthesized according to the same procedure as that of 1N-PPP. Black solid of 1N-PSP was obtained in 61% yield, mp: 260–262C.1H NMR (DMSO-d 6):
d
8.17 (s, 1H), 8.00 (d, 3H, J¼7.7 Hz), 7.91 (d, 1H, J¼8.3 Hz), 7.80–7.83 (m, 3H), 7.67 (d, 1H, J¼3.9 Hz), 7.37–7.59 (m, 7H), 7.26 (t, 2H, J¼7.9 Hz), 6.99–7.03 (m, 3H), 6.86 (d, 2H, J¼8.7 Hz).13C NMR (DMSO-d6):d
164.2, 151.9, 148.2, 147.4, 145.1, 142.5, 140.2, 137.6, 135.3, 131.6, 129.8, 129.0, 127.4, 127.1, 127.0, 126.8, 125.6, 123.1, 122.7, 120.8, 117.6, 105.8. HRMS (m/z): 548.1555 (Mþ) (calcd for C 36H24N2O2S: 548.1158). Anal. Calcd for C36H24N2O2S: C, 78.81; H, 4.41; N, 5.11; O, 5.83; S, 5.84. Found: C, 78.77; H, 4.45; N, 5.09; O, 5.85; S, 5.84. 3.7. (E)-2-Cyano-3-(50-(500-(p-(naphthylphenylamino)phenyl)-thiophen-200-yl)-thiophen-20-yl)acrylic acid (1N-PSS)
Compound 1N-PSS was synthesized according to the same procedure as that of 1N-PPP. Black solids of 1N-PSS were obtained in 67% yield, mp: 253–255C.1H NMR (DMSO-d 6):
d
8.28 (s, 1H), 7.98 (d, 1H, J¼8.1 Hz), 7.89 (d, 1H, J¼8.2 Hz), 7.78–7.81 (m, 2H), 7.54 (t, 1H, J¼7.8 Hz), 7.44–7.49 (m, 5H), 7.39 (t, 1H, J¼7.6 Hz), 7.33 (d, 2H, J¼4.5 Hz), 7.23 (t, 2H, J¼7.8 Hz), 6.96–7.01 (m, 3H), 6.81 (d, 2H, J¼8.6 Hz).13C NMR (DMSO-d6):d
164.6, 148.4, 147.3, 145.4, 144.5, 144.3, 142.5, 139.9, 135.3, 134.5, 133.4, 130.9, 129.9, 129.0, 128.2, 127.7, 127.5, 127.2, 127.1, 126.9, 126.8, 125.8, 124.8, 124.3, 123.6, 123.2, 122.9, 120.5, 118.0, 102.7. HRMS (m/z): 554.1135 (Mþ) (calcdfor C34H22N2O2S2: 554.1123). Anal. Calcd for C34H22N2O2S2: C,
73.62; H, 4.00; N, 5.05; O, 5.77; S, 11.56. Found C, 73.59; H, 4.05; N, 5.07; O, 5.76; S, 11.53.
3.8. (E)-2-Cyano-3-(50-(500
-(5%-(naphthylphenylamino)-thiophen-2%-yl)thiophen-200-yl)thiophen-20-yl)acrylic
acid (1N-SSS)
Compound 1N-SSS was synthesized according to the same procedure as that of 1N-PPP. Black solid of 1N-SSS was obtained in 55% yield, mp: 259–261C.1H NMR (DMSO-d 6):
d
8.30 (s, 1H), 7.99 (d, 1H, J¼8.1 Hz), 7.93 (d, 1H, J¼8.2 Hz), 7.86 (d, 1H, J¼8.2 Hz), 7.78 (d, 1H, J¼3.6 Hz), 7.46–7.58 (m, 4H), 7.40 (dd, 1H, J¼3.8, 0.9 Hz), 7.37 (dd, 1H, J¼3.8, 0.9 Hz), 7.20 (t, 2H, J¼7.5 Hz), 7.09 (dd, 1H, J¼3.8, 0.9 Hz), 7.06 (dd, 1H, J¼3.8, 0.9 Hz), 6.93 (d, 3H, J¼7.9 Hz), 6.50 (dd, 1H, J¼3.9, 1.0 Hz).13C NMR (DMSO-d6):d
164.3, 152.5, 148.0, 145.0, 144.6, 142.4, 140.5, 138.9, 135.2, 134.4, 132.9, 130.3, 130.0, 129.8, 129.1, 128.2, 128.1, 127.5, 127.3, 127.0, 124.9, 124.6, 124.5, 123.2, 122.5, 119.4, 118.3, 117.7, 101.2. HRMS (m/z): 560.0694 (Mþ) (calcdfor C32H20N2O2S3: 560.0687). Anal. Calcd for C32H20N2O2S3: C,
68.55; H, 3.60; N, 5.00; O, 5.71; S, 17.16. Found: C, 68.60; H, 3.63; N, 4.98; O, 5.73; S, 17.15.
3.9. (E)-2-Cyano-3-(diphenylaminotriphenylene)acrylic acid (1P-PPP)
Compound 1P-PPP was synthesized according to the same procedure as that of 1N-PPP. The orange solid of 1P-PPP was obtained in 64% yield, mp: 256–258C.1H NMR (DMSO-d
6):
d
8.33 (s, 1H), 8.11 (d, 2H, J¼8.5 Hz), 7.92 (d, 2H, J¼8.5 Hz), 7.83 (d, 2H, J¼8.5 Hz), 7.73 (d, 2H, J¼8.5 Hz), 7.63(d, 2H, J¼6.8 Hz), 7.29 (t, 4H, J¼7.0 Hz), 7.00–7.06 (m, 8H).13C NMR (DMSO-d6):d
163.7, 154.1, 400 500 600 700 800 0 20 40 60 80 1P-PPP1P-PPS 1P-PSP 1P-PSS 1P-SSS IPCE (%) Wavelength (nm) 1N-PPP 1N-PPS 1N-PSP 1N-PSS 1N-SSS N719147.4, 147.3, 144.2, 140.1, 137.2, 133.2, 131.8, 130.8, 130.0, 127.9, 127.8, 127.4, 124.7, 123.8, 123.4, 116.7, 103.4. HRMS (m/z): 492.1830 (Mþ)
(calcd for C34H24N2O2: 492.1838). Anal. Calcd for C34H24N2O2: C,
82.91; H, 4.91; N, 5.69; O, 6.50. Found: C, 82.87; H, 4.93; N, 5.65; O, 6.55.
3.10. (E)-2-Cyano-3-(50
-(diphenylaminobiphenylene)-thiophen-20-yl)acrylic acid (1P-PPS)
Compound 1P-PPS was synthesized according to the same procedure as that of 1N-PPP. Black solid of 1P-PPS was obtained in 61% yield, mp: 267–269C.1H NMR (DMSO-d 6):
d
8.05 (s, 1H), 7.95 (d, 2H, J¼7.4 Hz), 7.80 (d, 2H, J¼8.2 Hz), 7.66 (d, 1H, J¼3.7 Hz), 7.59 (d, 2H, J¼8.7 Hz), 7.44 (d, 1H, J¼3.8 Hz), 7.31 (t, 4H, J¼7.9 Hz), 7.02– 7.08 (m, 6H), 6.96 (d, 2H, J¼8.7 Hz).13C NMR (DMSO-d6):d
164.3, 148.3, 147.5, 147.1, 144.4, 140.8, 136.4, 132.0, 130.8, 130.0, 127.5, 126.9, 126.8, 125.6, 124.8, 124.6, 123.9, 123.2, 119.1. HRMS (m/z): 498.1395 (Mþ) (calcd for C32H22N2O2S: 498.1402). Anal. Calcd for
C32H22N2O2S: C, 77.09; H, 4.45; N, 5.62; O, 6.42; S, 6.43. Found: C,
77.13; H, 4.49; N, 5.59; O, 6.45; S, 6.34.
3.11. (E)-2-Cyano-3-(p-(50
-(p-diphenylamino)phenyl)-thiophen-20-yl)phenyl)acrylic acid (1P-PSP)
Compound 1P-PSP was synthesized according to the same procedure as that of 1N-PPP. Black solid of 1P-PSP was obtained in 70% yield, mp: 262–264C.1H NMR (DMSO-d 6):
d
8.22 (s, 1H), 7.80 (d, 1H, J¼3.7 Hz), 7.77 (d, 2H, J¼8.3 Hz), 7.71 (d, 2H, J¼8.3 Hz), 7.67 (d, 1H, J¼3.7 Hz), 7.62 (d, 2H, J¼8.5 Hz), 7.30 (t, 4H, J¼7.6 Hz), 6.99– 7.06 (m, 8H).13C NMR (DMSO-d6):d
164.2, 149.1, 147.5, 147.3, 140.3, 137.6, 136.2, 133.1, 131.6, 130.0, 127.9, 127.2, 126.8, 124.9, 124.7, 123.8, 123.4, 119.1. HRMS (m/z): 498.1395 (Mþ) (calcd for C32H22N2O2S:498.1402). Anal. Calcd for C32H22N2O2S: C, 77.09; H, 4.45; N, 5.62; O,
6.42; S, 6.43. Found: C, 77.03; H, 4.51; N, 5.57; O, 6.49; S, 6.40.
3.12. (E)-2-Cyano-3-(50-(500
-(p-(diphenylamino)phenyl)-thiophen-200-yl)thiophen-20-yl)acrylic acid (1P-PSS)
Compound 1P-PSS was synthesized according to the same procedure as that of 1N-PPP. Black solid of 1P-PSS was obtained in 69% yield, mp: 266–268C.1H NMR (DMSO-d 6):
d
8.24 (s, 1H), 7.74 (d, 1H, J¼3.8 Hz), 7.50 (d, 2H, J¼8.4 Hz), 7.44 (d, 1H, J¼3.7 Hz), 7.41 (d, 1H, J¼3.8 Hz), 7.35 (d, 1H, J¼3.8 Hz), 7.26 (t, 4H, J¼7.2 Hz), 7.02 (t, 4H, J¼7.2 Hz), 6.97 (d, 2H, J¼7.5 Hz), 6.87 (d, 2H, J¼7.5 Hz).13C NMR (DMSO-d6):d
164.7, 147.8, 147.0, 145.2, 144.4, 144.3, 139.9, 134.6, 133.7, 130.1, 128.1, 126.9, 126.8, 124.9, 124.8, 124.6, 124.1, 122.8, 118.0, 102.6. HRMS (m/z): 504.0967 (Mþ) (calcd for C30H20N2O2S2: 504.0966). Anal. Calcd for C30H20N2O2S2: C, 71.40;H, 3.99; N, 5.55; O, 6.34; S, 12.71. Found: C, 71.38; H, 4.01; N, 5.51; O, 6.37; S, 12.73.
3.13. (E)-2-Cyano-3-(50-(500
-(5%-(diphenylamino)-thiophen-2%-yl)thiophen-200-yl)thiophen-20-yl)acrylic acid (1P-SSS)
Compound 1P-SSS was synthesized according to the same procedure as that of 1N-PPP. Black solid of 1P-SSS was obtained in 60% yield, mp: 253–255C.1H NMR (DMSO-d 6):
d
8.31 (s, 1H), 7.80 (d, 1H, J¼4.1 Hz), 7.42 (d, 1H, J¼4.0 Hz), 7.41 (d, 1H, J¼3.9 Hz), 7.28 (t, 4H, J¼3.9 Hz), 7.14 (d, 1H, J¼3.93 Hz), 7.13 (d, 1H, J¼3.9 Hz), 7.05– 7.07 (m, 6H), 6.53 (d, 1H, J¼4.0 Hz).13C NMR (DMSO-d6):d
164.1, 151.7, 147.1, 145.7, 145.0, 141.1, 139.0, 134.3, 130.0, 128.6, 128.3, 125.1, 124.8, 124.6, 124.4, 123.2, 120.5, 117.4, 100.0. HRMS (m/z): 510.0537 (Mþ) (calcd for C28H28N2O2S3: 510.0530). Anal. Calcd forC28H18N2O2S3: C, 65.86; H, 3.55; N, 5.49; O, 6.27; S, 18.84. Found: C,
65.80; H, 3.60; N, 5.45; O, 6.31; S, 18.84.
3.14. 4-Bromo-40-(naphthylphenylamino)biphenyl (2N)
A mixture of 4,40-dibromobiphenyl (8.46 g, 27.4 mmol), Pd(OAc) 2
(105 mg, 0.18 mmol), dppf (253 mg, 0.46 mmol), N-(1-naphthyl)-aniline (2.0 g, 9.13 mmol), and sodium tert-butoxide (1.32 g, 13.7 mmol) in dry toluene was placed in a three-necked flask under a nitrogen atmosphere and was stirred at 90C for 15 h. After cooling,
the reaction was quenched by adding water and then was extracted with ethyl acetate. The organic layer was dried over anhydrous MgSO4and evaporated under vacuum. The products were purified by
silica gel column chromatograph eluted with hexane. White solid of 2N was obtained in 70% yield (2.86 g, 6.37 mmol). Spectroscopic data of 2N.1H NMR (CDCl3):
d
7.95 (d, 1H, J¼7.9 Hz), 7.90 (d, 1H, J¼7.9 Hz),7.79 (d, 1H, J¼8.2 Hz), 7.44–7.52 (m, 4H), 7.35–7.41 (m, 6H), 7.20–7.24 (m, 2H), 7.03–7.11 (m, 4H), 6.97 (t, 1H, J¼7.3 Hz).13C NMR (CDCl3):
d
148.1, 147.9, 143.1, 139.5, 135.2, 132.5, 131.7, 131.2, 129.1, 128.4, 128.0, 127.4, 127.2, 126.6, 126.4, 126.3, 126.1, 124.1, 122.3, 122.1, 121.3, 120.6. FAB HRMS (m/z): 449.0783 (Mþ) (calcd for C28H20BrN: 449.0779).
3.15. 4-Bromo-40-diphenylaminobiphenyl (2P)
Compound 2P was synthesized according to the same procedure as that of 2N, giving 2P in 80% yield as yellow solid. Spectroscopic data for 2P.1H NMR (CDCl3):
d
7.52 (d, 2H, J¼8.6 Hz), 7.42 (dd, 4H, J¼8.7, 1.3 Hz), 7.26 (dd, 4H, J¼6.8, 1.8 Hz), 7.12 (dt, 6H, J¼8.7, 1.8 Hz), 7.02 (d, 2H, J¼7.3 Hz).13C NMR (CDCl3):d
147.5, 139.5, 133.5, 131.7, 129.3, 129.2, 128.1, 127.4, 124.5, 124.3, 123.6, 123.0, 120.8. FAB HRMS (m/z): 399.0633 (Mþ) (calcd for C 24H18BrN: 339.0623). 3.16. 40 -(Naphthylphenylamino)triphenylene-4-carbaldehyde (3N)To a three-necked round-bottom flask containing 2N (6.82 g, 15.2 mmol) was added dropwise BuLi (10 mL, 16.1 mmol, 1.6 M in hexane) in dry THF at 78C, after then solution was brought to 0C
and was stirred by a magnetic bar for 30 min. The solution was cooled again to 78C and to it was added dropwise triisopropylborate
(5.3 mL, 19.8 mmol). The reaction mixture was warmed up gradually to room temperature and was stirred overnight. To the reaction mixture was then added excess amount of 10% HCl(aq)(30 mL), while
the mixture was stirred for another 1 h. The reaction was quenched by pouring into distilled water, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous MgSO4. Evaporation of
the solvent gave a crude product, which was immediately subjected to the next reaction. It was mixed with p-bromobenzaldehyde (2.57 g, 14.0 mmol), K2CO3(aq)(2.76 g, 2 mmol) in 10 mL H2O, and Pd(PPh3)4
(807 mg, 0.69 mmol) in dry toluene/THF (2/1). The mixture was heated to 90C for 12 h. After cooling, the products were extracted
with ethyl acetate and the organic layer dried over anhydrous MgSO4.
The crude product was dried in vacuo, and was purifies by silica gel column chromatograph eluted with CH2Cl2/hexane (1/1). Yellow
solid of 3N was obtained in 88% yield (6.35 g, 13.4 mmol). Spectro-scopic data for 3N.1H NMR (CDCl3):
d
10.04 (s, 1H), 7.93–7.95 (m, 3H),7.88 (d,1H, J¼8.1 Hz), 7.78 (t, 3H, J¼6.9 Hz), 7.67 (d, 2H, J¼8.6 Hz), 7.64 (d, 2H, J¼8.6 Hz), 7.44–7.50 (m, 4H), 7.35–7.38 (m, 2H), 7.24 (d, 1H, J¼4.2 Hz), 7.21 (d, 2H, J¼7.2 Hz), 7.10 (d, 2H, J¼8.6 Hz), 7.07 (d, 2H, J¼8.6 Hz), 6.96 (t,1H, J¼7.2 Hz);13C NMR (CDCl3):
d
191.7,148.2,148.0, 146.6, 143.3, 140.8, 137.6, 135.3, 135.1, 132.8, 131.3, 130.3, 129.2, 128.5, 127.7, 127.6, 127.3, 127.0, 126.7, 126.4, 124.5, 124.2, 122.4, 122.3, 121.5. FAB HRMS (m/z): 475.1933 (Mþ) (calcd for C35H25NO: 475.1936).
3.17. 40-(Diphenylamino)triphenylene-4-carbaldehyde (3P)
Compound 3P was synthesized according to the same procedure as that of 3N, giving 3P in 90% yield as yellow solid. Spectroscopic data for 3P.1H NMR (CDCl3):
d
10.62 (s, 1H), 7.96 (d, 2H, J¼8.2 Hz),7.80 (d, 2H, J¼8.2 Hz), 7.67–7.72 (m, 4H), 7.52 (d, 2H, J¼8.6 Hz), 7.25–7.31 (m, 5H), 7.14–7.17 (m, 5H), 7.02 (t, 2H, J¼7.3 Hz).13C NMR (CDCl3):
d
191.8, 147.6, 147.5, 146.6, 140.7, 137.8, 135.0, 133.8, 130.2, 129.2, 127.6, 127.3, 127.0, 124.5, 123.6, 123.0. FAB HRMS (m/z): 426.1859 (Mþ) (calcd for C 31H23NO: 426.1858). 3.18. 5-(Naphthylphenylamino)biphenylenethiophene-2-carbaldehyde (4N)Compound 4N was synthesized according to the same pro-cedure as that of 3N, giving 4N in 80% yield as yellow solid. Spec-troscopic data for 4N.1H NMR (CDCl3):
d
9.88 (s, 1H), 7.98 (d, 1H,J¼8.4 Hz), 7.91 (d, 1H, J¼8.2 Hz), 7.81 (d, 1H, J¼8.2 Hz), 7.71 (d, 1H, J¼4.0 Hz), 7.69 (d, 2H, J¼8.4 Hz), 7.59 (d, 2H, J¼8.4 Hz), 7.36–7.52 (m, 7H), 7.22–7.26 (m, 2H), 7.13 (d, 2H, J¼7.6 Hz), 7.07 (d, 2H, J¼8.6 Hz), 7.00 (t, 1H, J¼7.3 Hz).13C NMR (CDCl3):
d
182.6, 154.1, 148.3, 147.9, 143.1, 142.1, 141.6, 137.4, 135.3, 132.3, 131.2, 131.1, 129.2, 128.4, 127.4, 127.3, 126.9, 126.7, 126.5, 126.3, 126.2, 124.1, 123.7, 122.5, 122.3, 121.2. FAB HRMS (m/z): 481.1505 (Mþ) (calcd for C33H23NOS: 481.1500).3.19. 5-(Diphenylaminobiphenylene)thiophene-2-carbaldehyde (4P)
Compound 4P was synthesized according to the same procedure as that of 3N, giving yellow solid of 4P in 88% yield.1H NMR (CDCl3):
d
9.89 (s, 1H), 7.74 (d, 1H, J¼3.9 Hz), 7.72 (d, 2H, J¼8.4 Hz), 7.63 (d, 2H, J¼8.4 Hz), 7.50 (d, 2H, J¼8.6 Hz), 7.42 (d, 1H, J¼3.9 Hz), 7.25– 7.30 (m, 4H), 7.13–7.15 (m, 6H), 7.05 (t, 2H, J¼7.3 Hz).13C NMR (CDCl3):d
182.0, 154.0, 147.7, 147.4, 142.1, 141.6, 137.4, 133.3, 131.3,129.3, 127.5, 127.1, 126.7, 124.6, 123.8, 123.4, 123.1. FAB HRMS (m/z): 431.1349 (Mþ) (calcd for C29H21NOS: 431.1344).
3.20. p-Bromo-N-naphthyl-N-phenylaniline (5N)
Compound 5N was synthesized according to the same pro-cedure as that of 2N, giving white solid of product 5N in 65%.1H NMR (CDCl3):
d
7.86 (d, 2H, J¼9.17 Hz), 7.76 (d, 1H, J¼8.1 Hz), 7.45 (t,2H, J¼7.8 Hz), 7.34 (t, 1H, J¼7.8 Hz), 7.28 (d, 1H, J¼7.3 Hz), 7.16–7.25 (m, 4H), 7.02 (d, 2H, J¼7.7 Hz), 6.94 (t, 1H, J¼7.3 Hz), 6.84 (dt, 2H, J¼8.9, 2.6 Hz).13C NMR (CDCl3):
d
147.8, 147.5, 142.9, 135.2, 131.9,130.9, 129.2, 128.4, 127.1, 126.7, 126.5, 126.3, 126.2, 123.9, 122.7, 122.3, 122.2, 113.5. FAB HRMS (m/z): 373.0475 (Mþ) (calcd for
C22H16BrN: 373.0466).
3.21. p-Bromo-N,N-diphenylaniline (5P)
Compound 5P was synthesized according to the same procedure as that of 2N, giving white solid of product 5P in 65% yield.1H NMR (CDCl3):
d
7.32 (t, 2H, J¼8.8 Hz), 7.20–7.29 (m, 4H), 7.05 (t, 4H, J¼7.3 Hz), 6.96–7.02 (m, 2H), 6.90–6.93 (m, 2H).13C NMR (CDCl3):d
147.3, 146.9, 132.1, 129.3, 125.0, 124.3, 123.1, 114.7. FAB HRMS (m/z): 323.0309 (Mþ) (calcd for C 18H14BrN: 323.0310). 3.22. N-Naphthyl-N-phenyl-p-(20-thiophenyl)aniline (6N)To a three-necked flask containing a mixture of 5N (2.3 g, 6.19 mmol), PdCl2(PPh3)2 (0.13 g, 0.18 mmol), and
2-tributyl-stannylthiophene (5.3 mL, 14.2 mmol) was added DMF (20 mL). The reaction mixture was stirred at 90C for 24 h. After cooling, the
reaction was quenched by adding MeOH and KF(aq) (saturated
15 mL). The mixture was extracted with CH2Cl2 and the organic
layer dried over anhydrous MgSO4. Evaporation of the solvent gave
the crude, which was purified by silica gel with hexane as eluent. The white solid in 78% yield (1.82 g, 4.82 mmol). Spectroscopic data for 6N.1H NMR (CDCl3):
d
7.93 (d, 1H, J¼8.2 Hz), 7.88 (d, 1H, J¼8.2 Hz), 7.78 (d, 1H, J¼8.2 Hz), 7.33–7.49 (m, 6H), 7.17–7.23 (m, 4H), 6.94–7.08 (m, 6H).13C NMR (CDCl3):d
148.0, 147.8, 144.3, 143.1, 135.2, 131.1, 129.1, 128.3, 127.8, 127.1, 126.6, 126.5, 126.4, 126.3, 124.1, 123.7, 122.2, 122.0, 121.9, 121.4. FAB HRMS (m/z): 377.1212 (Mþ) (calcd for C26H19NS: 377.1204). 3.23. N,N-Diphenyl-p-(20-thiophenyl)aniline (6P)Product 6P was synthesized according to the procedure as 6N, giving a white solid of product 6P in 80%. Spectroscopic data for 6P.
1H NMR (CDCl 3):
d
7.46 (d, 2H, J¼8.6 Hz), 7.25 (d, 2H, J¼7.5 Hz), 7.24 (d, 2H, J¼7.4 Hz), 7.19–7.21 (m, 2H), 7.10 (d, 4H, J¼7.5 Hz), 7.05 (d, 2H, J¼8.4 Hz), 7.00–7.03 (m, 3H).13C NMR (CDCl3):d
147.4, 147.1, 144.2, 129.2, 128.5, 127.9, 126.6, 124.4, 123.9, 123.7, 122.9, 122.1. FAB HRMS (m/z): 327.1084 (Mþ) (calcd for C 22H17NS: 327.1082). 3.24. p-(5-(p-(Naphthylphenylamino)phenyl)thiophen-2-yl)benzaldehyde (7N)To a three-necked flask containing a mixture of 6N (4.67 g, 12.4 mmol) in dry THF was adding dropwise BuLi (10 mL, 16.1 mmol, 1.6 M in hexane) at 78C, then the solution was
allowed to warm up gradually to 0C for ca. 30 min. The solution
was cooled again to 78C and to it was added dropwise
tri-n-butylchlorostannane (5.3 mL, 16.1 mmol). The reaction mixture was warmed up to room temperature and stirred overnight. The re-action mixture was quenched by the addition of water, and was extracted with CH2Cl2. The combined organic solution was dried
over anhydrous MgSO4and dried in vacuo. The crude product was
dissolved in dry DMF, to which were added p-bromobenzaldehyde (2.28 g, 12.38 mmol) and PdCl2(PPh3)2 (237 mg, 0.37 mmol). The
solution was heated to 90C for 24 h and then cooled. The reaction
was quenched by the addition of MeOH and KF(aq) (saturated
15 mL). The mixture was extracted with CH2Cl2, while the organic
layer was dried over anhydrous MgSO4. Evaporation of the solvent
gave a product, which was purified by silica gel column chro-matograph eluted with CH2Cl2/hexane (1/1). Compound 7N was
obtained in 75% yield (4.47 g, 9.3 mmol) as white solid. Spectro-scopic data for 7N.1H NMR (CDCl3):
d
9.97 (s, 1H), 7.91 (d, 1H,J¼8.6 Hz), 7.88 (d, 1H, J¼7.8 Hz), 7.84 (d, 2H, J¼8.4 Hz), 7.78 (d, 1H, J¼8.2 Hz), 7.72 (d, 2H, J¼8.2 Hz), 7.34–7.49 (m, 7H), 6.96–7.23 (m, 8H).13C NMR (CDCl3):
d
191.3, 148.4, 147.7, 146.1, 142.9, 140.3, 140.1,135.2, 134.7, 131.1, 130.4, 129.2, 128.4, 127.3, 126.8, 126.6, 126.5, 126.4, 126.3, 126.2, 126.0, 125.4, 124.0, 123.1, 122.6, 122.5, 121.0. FAB HRMS (m/z): 481.1498 (Mþ) (calcd for C33H23NOS: 481.1500).
3.25. p-(5-(p-(Diphenylamino)phenyl)thiophen-2-yl)-benzaldehyde (7P)
Product 7P was synthesized according to the procedure as 7N, giving a white solid of product 7P in 78%. Spectroscopic data for 7P.
1H NMR (CDCl 3):
d
10.00 (s, 1H), 7.89 (d, 2H, J¼8.5 Hz), 7.76 (d, 2H, J¼8.3 Hz), 7.51 (d, 2H, J¼8.7 Hz), 7.43 (d, 1H, J¼3.8 Hz), 7.27–7.31 (m, 4H), 7.24 (d, 1H, J¼3.8 Hz), 7.05–7.10 (m, 8H).13C NMR (CDCl3):d
191.3, 147.8, 147.2, 145.9, 140.61, 140.1, 134.8, 130.4, 129.3, 127.5, 126.5, 126.0, 125.4, 124.6, 123.4, 123.3, 123.2. FAB HRMS (m/z): 431.1342 (Mþ) (calcd for C 29H21NOS: 431.1344). 3.26. 5-(50-(p-(Naphthylphenylamino)phenyl)thiophen-20 -yl)thiophene-2-carbaldehyde (8N)Compound 8N was synthesized according to the same pro-cedure as that of 7N, giving orange solid of 8N in 68% yield.1H NMR (CDCl3):
d
9.82 (s, 1H), 7.97 (d, 1H, J¼8.4 Hz), 7.92 (d, 1H, J¼8.2 Hz),7.82 (d, 1H, J¼8.2 Hz), 7.57 (d, 1H, J¼4.0 Hz), 7.46–7.51 (m, 4H), 7.36– 7.40 (m, 4H), 7.26 (d, 1H, J¼4.0 Hz), 7.24 (d, 2H, J¼7.8 Hz), 7.16 (d, 1H,
J¼4.0 Hz), 7.14 (d, 2H, J¼7.6 Hz), 7.08 (d, 1H, J¼3.9 Hz), 7.03 (d, 1H, J¼7.3 Hz), 6.98 (d, 2H, J¼8.7 Hz).13C NMR (CDCl3):
d
182.3, 148.6,147.4, 146.3, 142.9, 141.1, 137.4, 135.3, 133.7, 131.1, 129.3, 128.5, 127.3, 127.2, 126.9, 126.6, 126.5, 126.4, 126.3, 126.1, 124.0, 123.6, 122.9, 122.8, 122.7, 120.9. FAB HRMS (m/z): 487.1068 (Mþ) (calcd for
C31H21NOS2: 487.1065).
3.27. 5-(50-(p-Diphenylaminophenyl)thiophen-20
-yl)-thiophene-2-carbaldehyde (8P)
Compound 8P was synthesized according to the same procedure as that of 7N, giving yellow solid of 8P in 68% yield.1H NMR (CDCl3):
d
9.84 (s, 1H), 7.65 (d, 1H, J¼3.9 Hz), 7.45 (d, 2H, J¼8.3 Hz), 7.22–7.31 (m, 6H), 7.04–7.17 (m, 9H).13C NMR (CDCl3):
d
182.3, 148.0, 147.3,147.2, 146.2, 141.2, 137.1, 134.0, 129.3, 127.1, 127.0, 126.5, 124.7, 123.6, 123.4, 123.1, 123.0. FAB HRMS (m/z): 437.0912 (Mþ) (calcd for C27H19NOS2: 437.0809).
3.28. 5-(50-(500-Bromothiophen-200-yl)thiophen-20
-yl)-2-(naphthylphenylamino)thiophene (9N)
Compound 9N was synthesized according to the same pro-cedure as that of 2N, giving yellow solid of 9N in 47% yield.1H NMR (CDCl3):
d
8.02 (d, 1H, J¼8.3 Hz), 7.86 (d, 1H, J¼8.2 Hz), 7.42–7.52 (m,4H), 7.21 (t, 2H, J¼7.9 Hz), 7.04 (d, 2H, J¼8.2 Hz), 6.85–6.97 (m, 6H), 6.52 (d, 1H, J¼4.0 Hz).13C NMR (CDCl3):
d
151.8, 148.5, 142.8, 138.7,137.2, 135.1, 134.0, 130.7, 130.6, 129.0, 128.4, 127.4, 126.7, 126.4, 126.3, 126.2, 125.7, 124.4, 123.8, 123.6, 123.0, 122.4, 121.6, 119.1, 118.5, 117.8, 110.6. FAB HRMS (m/z): 542.9774 (Mþ) (calcd for C28H18BrNS3: 542.9785).
3.29. 5-(50-(500-Bromothiophen-200-yl)thiophen-20
-yl)-2-diphenylaminothiophene (9P)
Compound 9P was synthesized according to the same procedure as that of 2N, giving yellow solid of 9P in 50% yield.1H NMR (CDCl3):
d
7.24–7.27 (m, 4H), 7.14–7.16 (m, 4H), 7.03 (t, 2H, J¼7.3 Hz), 6.94 (d, 1H, J¼3.8 Hz), 6.93 (d, 1H, J¼3.8 Hz), 6.91 (d, 1H, J¼3.8 Hz), 6.89 (d, 1H, J¼3.8 Hz), 6.85 (d, 1H, J¼3.8 Hz), 6.55 (d, 1H, J¼3.8 Hz).13C NMR (CDCl3):d
151.0, 147.4, 138.6, 137.1, 134.2, 130.6, 130.3, 129.2, 124.4, 123.4, 123.3, 123.2, 122.7, 122.4, 120.7, 110.7. FAB HRMS (m/z): 492.9628 (Mþ) (calcd for C24H16BrNS3: 492.9628). 3.30. 5-(50-(500-(Naphthylphenylamino)thiophen-200 -yl)-thiophen-20-yl)thiophene-2-carbaldehyde (10N)To a three-necked flask containing a solution of 9N (0.94 g, 1.73 mmol) in dry THF was added dropwise BuLi (1.6 mL, 2.6 mmol, 1.6 M in hexane) at 78C. The solution was allowed to warm up
gradually to 0C for about 30 min. The solution was cooled again to
78C, then to it was added dropwise DMF (0.2 mL, 2.6 mmol). The
reaction mixture was warmed up to room temperature and was stirred with a magnetic bar for overnight. The reaction was quenched by the addition of distilled water, and then was extracted with CH2Cl2. The organic layers were combined and dried over
anhydrous MgSO4. The solvent was evaporated in vacuo to yield
crude product, which was purified by silica gel column chromato-graph eluted with CH2Cl2/hexane (1/1). Compound 10P was
obtained as yellow solid in 72% yield (0.61 g, 1.24 mmol). Spectro-scopic data for 10N.1H NMR (CDCl3):
d
9.82 (s, 1H), 8.01 (d, 1H,J¼8.2 Hz), 7.91 (d, 1H, J¼8.0 Hz), 7.83 (d, 1H, J¼7.6 Hz), 7.61 (d, 1H, J¼4.0 Hz), 7.43–7.53 (m, 4H), 7.14–7.25 (m, 4H), 7.06–7.08 (m, 2H), 6.93–6.98 (m, 2H), 6.88 (d, 1H, J¼3.9 Hz), 6.49 (d, 1H, J¼3.9 Hz).13C NMR (CDCl3):
d
182.2, 152.8, 148.3, 147.0, 142.8, 141.2, 139.8, 137.3, 135.1, 133.2, 130.6, 129.1, 128.4, 127.8, 127.5, 126.9, 126.8, 126.4, 126.3, 126.2, 123.6, 123.5, 123.3, 123.2, 121.9, 119.5, 117.8. FAB HRMS (m/z): 493.0620 (Mþ) (calcd for C 29H19NOS3: 493.0629). 3.31. 5-(50-(500-(Diphenylamino)thiophen-200-yl)thiophen-20 -yl)thiophene-2-carbaldehyde (10P)Compound 10P was synthesized according to the same pro-cedure as that of 10N, giving yellow solid of 10P in 60% yield.1H NMR (CDCl3):
d
9.81 (s, 1H), 7.60 (d, 1H, J¼4.0 Hz), 7.26–7.29 (m,4H), 7.15–7.19 (m, 6H), 7.0 (t, 2H, J¼7.3 Hz), 6.97 (d, 1H, J¼3.6 Hz), 6.93 (d, 1H, J¼3.8 Hz), 6.55 (d, 1H, J¼3.8 Hz).13C NMR (CDCl3):
d
182.2, 152.0, 147.4, 146.9, 141.3, 139.7, 137.3, 133.5, 129.3, 123.8, 123.7, 123.6, 123.0, 120.1. FAB HRMS (m/z): 443.0472 (Mþ) (calcd forC25H17NOS3: 443.0472).
Acknowledgements
This work was supported by the National Science Council and Academia Sinica of the Republic of China.
Supplementary data
Solvent-dependent absorption spectra of 1P-PSP and 1P-SSS, TDDFT calculated orbitals, Mulliken charges, and low energy tran-sitions of selected compounds, 1H and 13C NMR spectra of all compounds. Supplementary data associated with this article can be found in the online version at doi:10.1016/j.tet.2009.04.024.
References and notes
1. (a) Chen, J.; Reed, M. A.; Rawlett, A. M.; Tour, J. M. Science 1999, 286, 1550; (b) Metzger, R. M. J. Mater. Chem. 2000, 10, 55; (c) Yu, C. J.; Chong, Y.; Kayyem, J. F.; Gozin, M. J. Org. Chem. 1999, 64, 2070.
2. (a) Chow, T. J.; Pan, Y.-T.; Yeh, Y.-S.; Wen, Y.-S.; Chen, K.-Y.; Chou, P.-T. Tetra-hedron 2005, 61, 6967; (b) Chen, K.-Y.; Hsieh, C.-C.; Cheng, Y.-M.; Lai, C.-H.; Chou, P.-T.; Chow, T. J. J. Phys. Chem. A 2006, 110, 12136; (c) Chow, T. J.; Chen, H.-C.; Chiu, N.-R.; Chen, C.-Y.; Yu, W.-S.; Cheng, Y.-M.; Cheng, C.-C.; Chang, C.-P.; Chou, P.-T. Tetrahedron 2003, 59, 5719.
3. (a) Wang, Z.-S.; Cui, Y.; Hara, K.; Dan-oh, Y.; Kasada, C.; Shinpo, A. Adv. Mater. 2007, 19, 1138; (b) Hara, K.; Miyamoto, K.; Abe, Y.; Yanagida, M. J. Phys. Chem. B 2005, 109, 23776.
4. Kuang, D.; Uchida, S.; Humphry-Baker, R.; Zakeeruddin, S. M.; Gra¨tzel, M. An-gew. Chem., Int. Ed. 2008, 47, 1923.
5. (a) Ehret, A.; Stuhl, L.; Spitler, M. T. J. Phys. Chem. B 2001, 105, 9960; (b) Sayama, K.; Hara, K.; Ohga, Y.; Shinpou, A.; Suga, S.; Arakawa, H. New J. Chem. 2001, 25, 200.
6. Sayama, K.; Tsukagoshi, S.; Hara, K.; Ohga, Y.; Shinpou, A.; Abe, Y.; Suga, S.; Arakawa, H. J. Phys. Chem. B 2002, 106, 1363.
7. (a) Yao, Q.-H.; Shan, L.; Li, F.-Y.; Yin, D.-D.; Huang, C.-H. New J. Chem. 2003, 27, 1277; (b) Yao, Q.-H.; Meng, F.-S.; Li, F.-Y.; Tian, H.; Huang, C.-H. J. Mater. Chem. 2003, 13, 1048.
8. (a) Eu, S.; Hayashi, S.; Umeyama, T.; Oguro, A.; Kawasaki, M.; Kadota, N.; Matano, Y.; Imahori, H. J. Phys. Chem. C 2007, 111, 3528; (b) Cid, J.-J.; Yum, J.-H.; Jang, S.-R.; Nazeeruddin, M. K.; Martı´nez-Ferrero, E.; Palomares, E.; Ko, J.; Gra¨tzel, M.; Torres, T. Angew. Chem., Int. Ed. 2007, 46, 8358.
9. (a) Hagberg, D. P.; Yum, J.-H.; Lee, H.; De Angelis, F.; Marinado, T.; Karlsson, K. M.; Humphry-Baker, R.; Sun, L.; Hagfeldt, A.; Gra¨tzel, M.; Nazeeruddin, Md. K. J. Am. Chem. Soc. 2008, 130, 6259; (b) Liu, B.; Zhu, W.; Zhang, Q.; Wu, W.; Xu, M.; Ning, Z.; Xie, Y.; Tian, H. Chem. Commun. 2009, 1766; (c) Ning, Z.; Zhang, Q.; Wu, W.; Pei, H.; Liu, B.; Tian, H. J. Org. Chem. 2008, 73, 3791.
10. Urgaonkar, S.; Nagarajan, M.; Verkade, J. G. J. Org. Chem. 2003, 68, 452. 11. Gilchrist, T. L. J. Chem. Soc., Perkin Trans. 1 2001, 2491.
12. Suzuki, A. J. Organomet. Chem. 1999, 576, 147. 13. Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508. 14. Knoevenagel, E. Angew. Chem., Int. Ed. Engl. 1922, 35, 29.
15. Justin Thomas, K. R. J.; Hsu, Y.-C.; Lin, J.-T.; Lee, K.-M.; Ho, K.-C.; Lai, C.-H.; Cheng, Y.-M.; Chou, P. T. Chem. Mater. 2008, 20, 183.
