Pyrene functionalized triphenylamine-based dyes: synthesis, photophysical properties and applications in OLEDs.

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Organic & Biomolecular Chemistry Accepted Manuscript This article can be cited before page numbers have been issued, to do this please use: Y. Zhan, J. Peng, K. Ye, P. Xue and R. Lu, Org. Biomol. Chem., 2013, DOI: 10.1039/C3OB41185K.

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Pyrene functionalized triphenylamine-based dyes: synthesis, photophysical

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properties and applications in OLEDs Yong Zhan, Jiang Peng, Kaiqi Ye*, Pengchong Xue, Ran Lu* 5

Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X DOI: 10.1039/b000000x

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Pyrene functionalized triphenylamine-based dyes TP, TCP and TCCP were synthesized via alternately Heck and Wittig reactions. It was found that they could emit strong green light with high fluorescence yields because the formation of the excimer from pyrene unit was suppressed completely. Moreover, the non-doped organic light-emitting diodes using TP, TCP and TCCP as the emitters as well as the holetransporting materials were fabricated, and gave green electroluminescence. Notably, the device based on TP exhibited good performance with a low turn-on voltage of 2.80 V, a high maximum luminance of 29880 cd/m2 at 9.5 V, a high current efficiency of 3.34 cd/A, and a high power efficiency of 2.67 lm/w. It suggested that pyrene functionalized triphenylamine derivatives may have application in non-doped OLEDs.

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Introduction

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Emitting organic compounds with extended π-conjugated system have received much attention due to their promising applications in OLEDs,1 solid-state lasers,2 sensors,3 fluorescence imaging,4 and nonlinear optical materials.5 It is known that in the field of organic light-emitting diodes (OLEDs), developing new emitting materials as well as optimizing the device architectures can realize full-color, flat-panel displays with improved efficiency and lifetime.6 Up to date, a great number of functional πconjugated polymers,7 oligomers8 and dendrimers9 have been synthesized, and applied in OLEDs. Due to its strong fluorescence emission and fast charge-transport ability, pyrene is widely used as building block for organic optoelectronic materials applied in organic electronic devices, particularly in organic light-emitting diodes (OLEDs).10-13 However, excimer is usually formed from pyrene derivatives in concentrated solution or in the film,14 which would be detrimental to OLEDs.15 In order to suppress the formation of the excimer of pyrene-based materials, various molecular design strategies have been proposed, including the introduction of non-planar, twisted architectures.16 It should be noted that triphenylamine possesses a non-planar conformation, and it can be used as hole carriers in OLEDs.17 Therefore, we designed and synthesized new pyrene functionalized triphenylamine derivatives bridged by carbazole3-vinylene (TP, TCP and TCCP, Chart 1). It was found that the obtained compounds could emit strong green light, and no emission from the excimer based on pyrene unit was detected in solution or in the film. The OLEDs based on a configuration structure of [ITO/PEDOT:PSS/pyrene functionalized triphenylamine derivatives (45 nm)/Alq3 (55 nm)/LiF/Al] were This journal is © The Royal Society of Chemistry [year]

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prepared. Notably, the device based on TP exhibited a good performance with a low turn-on voltage of 2.8 V, a high maximum luminance of 29880 cd/m2 at 9.5 V, a high current efficiency of 3.34 cd/A, and a high power efficiency of 2.67 lm/w. Therefore, these pyrene functionalized triphenylaminebased dyes might become candidates for green-emitting materials in OLEDs with high performance.

Chart 1. The molecular structures of triphenylamine-based dyes TP, TCP and TCCP.

Results and discussion [journal], [year], [vol], 00–00 | 1

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Scheme 1. The synthetic routes for the brominated compounds 1, 3 and 6.

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Scheme 2. Syntheses of pyrene functionallized triphenylamine-based dyes TP, TCP and TCCP.

Synthesis

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The synthetic routes for compounds TP, TCP, and TCCP are sketched in Scheme 1 and 2. The compounds (4bromobenzyl)triphenylphosphonium bromide, 6-iodo-9-octyl9H-carbazole-3-carbaldehyde, 4-(N,N-diphenylamino) benzaldehyde, N-phenyl-N-(4-vinylphenyl)benzenamine and 1vinylpyrene were synthesized according to the reported procedures.18,28 Firstly, the Wittig reaction between 4-(N,Ndiphenylamino) benzaldehyde and (4bromobenzyl)triphenylphosphonium bromide afforded compound 1 in a yield of 78%. Compound 2 was synthesized from Nphenyl-N-(4-vinylphenyl)benzenamine and 6-iodo-9-octyl-9Hcarbazole-3-carbaldehyde via Heck reaction catalyzed by Pd(OAC)2 at 110 °C for 10 h in a yield of 72%.19 The Wittig reaction between compound 2 and (4bromobenzyl)triphenylphosphonium bromide afforded compound 3 in a yield of 52%. Accordingly, we gained compound 4 through Wittig reaction between compound 2 and methyltriphenylphosphoniumiodine. Then, compound 5 was 2 | Journal Name, [year], [vol], 00–00

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afforded from compound 4 and 6-iodo-9-octyl-9H-carbazole-3carbaldehyde in a yield of 60% via Heck reaction, and it could be transferred into compound 6 under Wittig reaction condition in yields of 40%. Finally, the compounds of TP, TCP and TCCP were prepared via Heck reaction from compounds 1, 3 and 6 catalyzed by Pd(OAC)2 at 110 °C for 12 h in yields of 65%, 62%, 54%, respectively. All the intermediates and the final products were purified by column chromatography, and the new compounds were characterized with FT-IR, 1H NMR, 13C NMR, elemental analysis, and MALDI/TOF mass spectroscopy. In the FT-IR spectra of compounds 1-6, TP, TCP and TCCP, the vibration absorption bands appeared at ca. 960 cm-1, suggesting C=C bond was in trans-form.20 In addition. 1H NMR spectra of TP, TCP and TCCP also confirmed that C=C groups adopted the trans-conformaion on account of the absence of the signal at ~6.5 ppm assigned to the protons in cis-double bonds (CH=CH).21,22 The obtained compounds TP, TCP and TCCP were readily dissolved in dichloromethane, chloroform, ethyl This journal is © The Royal Society of Chemistry [year]


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acetate and tetrahydrofuran.

Fig. 1 (a) UV-vis absorption and (b) fluorescent emission spectra (λex = 400 nm) of TP, TCP and TCCP in THF (1.0 × 10-6 M). 5

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The UV-vis absorption and fluorescence spectra of TP, TCP and TCCP in THF (1.0 × 10-6 M) are shown in Fig. 1, and the corresponding photophysical data are listed in Table 1. The maximal absorption peaks of TP, TCP and TCCP were located at 416, 408, and 401 nm, respectively, which could be ascribed to the π-π* transition of the molecular backbone.23 It should be noted that the maximum absorption peak blue-shifted as the length of molecular chain increased in solution. The reason might be that the coplanarity of compounds might decrease with increasing the length of molecules. In addition, TP emitted intense green fluorescence with a maximum at 518 nm when

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excited at 400 nm (Fig. 1b). With the increase in the number of carbazole unit, the fluorescent emission bands of TCP and TCCP blue-shifted to 506 nm and 504 nm, respectively. This may be ascribed to the same reason for the absorption spectral changes of TP, TCP and TCCP. The fluorescence quantum yields of TP, TCP and TCCP in degassed cyclohexane were 0.65, 0.52, 0.59, respectively, using 9,10-diphenylanthracene (DPA, Φ = 0.95, in cyclohexane) as a standard.24 It was clear the fluorescence quantum yield of TP was the highest among the three compounds because the exciton was confined to the whole backbone of the molecule.25

Fig. 2 Normalized (a) UV-vis absorption and (b) fluorescent emission spectra (λex = 400 nm) of TP, TCP and TCCP in the film.

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Fig. 2 shows the UV-vis absorption and fluorescent emission spectra of TP, TCP and TCCP in the films obtained via spinning the chloroform solutions (10 mg/mL) onto quartz slides. It was found that the maximum absorption peaks appeared at 382, 388 and 388 nm for TP, TCP, TCCP, respectively, in the film. The blue-shift of 34 nm, 20 nm, and 13 nm for TP, TCP, TCCP This journal is © The Royal Society of Chemistry [year]

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compared with those in solution was presumably caused by the formation of H-aggregates.26 TP, TCP and TCCP in the film gave maximal emission peaks at 512 nm, 528 nm, and 522 nm, respectively, and we did not observe the emission from the excimer of pyrene. In addition, we found that the maximal emission peaks of TP, TCP and TCCP did not shift at different Journal Name, [year], [vol], 00–00 | 3



Photophysical Properties


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aggregation of pyrene units, resulting in the suppression of the excimer formation. As to TCP and TCCP, the octyl groups in the bridges of carbazoles were almost vertical to the pyrene rings, which would restrain the stack of pyrene unit, so that the excimer formation from pyrene was suppressed. Therefore, these pyrene functionalized triphenylamine-based dyes were employed as emitting materials in OLEDs in the following discussion.

Fig. 3 (a) DSC and (b) TGA thermograms of TP, TCP, and TCCP under a nitrogen atmosphere at a heating/cooling rate of 10 °C/min.

Thermal Properties 20

The thermal properties of TP, TCP and TCCP were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) under a nitrogen atmosphere at a heating and cooling rate of 10 °C/min. As shown in Fig. 3 and Table 1, three compounds revealed high melting points (Tm) in the range of 159-236 °C. Their decomposition temperatures,

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which correspond to a 5% weight loss upon heating during TGA, were 369 °C for TP, 418 °C for TCP and 426 °C for TCCP. These results indicated that the thermal stabilities of three compounds were good, which would be helpful to improve stability and lifetime of devices.

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Table 1. Photophysical and thermal properties of TP, TCP and TCCP.

Compounds

TP TCP TCCP

Photoluminescenceb

Absorption

ΦFc

Tmd(°C)

Tde(°C)

Solutiona

Film

Solutiona

Film

273 , 288, 311 , 416 274 , 287, 311 338 , 382, 408 276, 290, 333, 383, 401

382 388, 411

518 506

512 528

0.65 0.52

214 236

369 418

388, 413

504

522

0.59

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426

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Measured in THF. b Excited at 400 nm. c The fluorescence quantum yields were determined against 9,10-diphenylanthracene in cyclohexane (ΦF = 0.95) as a standard excited at 392 nm. d Obtained from DSC measurement. e Obtained from TGA measurement (temperature at 5% weight loss under nitrogen, 10 °C /min ramp rate).

Electrochemical properties

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concentrations (Fig. S1), indicating that the excimer based on pyrene unit was suppressed completely. In order to reveal the reason why the formation of the excimer can be suppressed completely in the obtained dyes, we gave the optimized configurations of TP, TCP and TCCP calculated by the TDDFT/B3LYP/6-31G (d) level method on Gaussian 03 software in Supporting Information. As shown in Fig. S2, we could find that the nonplanar triphenylamine in TP might inhibit the

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DOI: 10.1039/C3OB41185K

compounds are comparable to those of widely used holetransporting materials (for example, NPB, 4,4’-bis(1naphthylphenylamino)biphenyl: HOMO, -5.2 eV; LUMO, -2.2 eV),27 therefore, these compounds might be used as holetransporting materials in OLEDs.


Molecular orbital calculations

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Fig. 4 Cyclic voltammetry diagrams of TP, TCP and TCCP in anhydrous CH2Cl2 with 0.1 M Bu4NPF6 as electrolyte at a scan rate of 100 mV/s.

The electrochemical behaviors of TP, TCP and TCCP were examined by cyclic voltammetry (CV) using a standard threeelectrode cell and an electrochemistry workstation (CHI 604) under N2 atmosphere. Platinum button was used as the working electrode, a platinum wire as the counter electrode, Ag/AgCl as the reference electrode, and ferrocene was used as a standard. The cyclic voltammetry (CV) diagrams of TP, TCP and TCCP in CH2Cl2 in the presence of TBAPF6 as the supporting electrolyte are shown in Fig. 4, and the corresponding electrochemical data are listed in Table 2. The three compounds displayed an irreversible redox process with onset oxidation peaks at +0.56, +0.46 and +0.49 V, respectively. On the basis of the first oxidation potential, the highest occupied molecular orbital (HOMO) energy levels can be estimated as -5.04 eV for TP, -4.94 eV for TCP and -4.97 eV for TCCP. The lowest unoccupied molecular orbital (LUMO) energy level of these compounds could be estimated from the HOMO energy level and energy band gap (Eg) as following the equation ： LUMO = HOMO + Eg. The LUMO energy levels are -2.41 eV, -2.31 eV, 2.35 eV for TP, TCP and TCCP, respectively. Notably, the HOMO levels of TP, TCP and TCCP are close to that of PEDOT:PSS (-5.2 eV), indicating a good hole injection contact. Furthermore, the HOMO and LUMO energy levels of these

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Fig. 5 The frontier orbital plots of the HOMO and LUMO of TP, TCP and TCCP.

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To gain a deeper insight into the electronic structures of these compounds, we carried out the density functional theory (DFT) calculation at the B3LYP/6-31G(d) level. To minimize calculation cost, the octyl group was replaced by methyl, and the corresponding energy levels are listed in Table 2. As shown in Fig. 5, the electron clouds of the HOMOs of TP, TCP and TCCP are mainly located at the triphenylamine and carbazole units, while electron density of LUMOs are primarily distributed on the benzene rings and pyrene units. It can be found from Table 2 that the extended conjugation results in high HOMO energy level, thereby the ability of hole-injection would be enhanced.

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Table 2. Electrochemical and theoretical calculational data.

Compounds Eonsetoxa(V) HOMOb(eV) LUMOb(eV) Egc(eV) HOMOd(eV) LUMOd(eV) 0.56 -5.04 -2.41 2.63 -4.76 -1.74 TP 0.46 -4.94 -2.31 2.63 -4.65 -1.69 TCP 0.49 -4.97 -2.35 2.62 -4.60 -1.66 TCCP a Eonsetox (V) = onset oxidation potential; potentials versus Ag/AgCl, working electrode platinum button, 0.1 M Bu4NPF6-CH2Cl2, scan rate 100 mV/s, Fc/Fc+ was used as external reference. b Calculated using the empirical equation: HOMO = -(4.48 + Eonsetox) and LUMO = HOMO + Eg. c Estimated from the onset of the absorption spectra (Eg = 1240/λonset). d Obtained from quantum chemical calculation using TDDFT/B3LYP/6-31G (d).

Electroluminescent Properties

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To evaluate the EL properties, three devices with similar structures, such as device 1 (ITO/PEDOT:PSS/TP(45 nm)/Alq3


(55 nm)/LiF/Al), device 2 (ITO/PEDOT:PSS/TCP (45 nm)/Alq3 (55 nm)/LiF/Al), device 3 (ITO/PEDOT:PSS/TCCP (45 nm)/Alq3 (55 nm)/LiF/Al), were fabricated. Compounds TP, Journal Name, [year], [vol], 00–00 | 5


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TCP and TCCP were used as emitters as well as holetransporting layer, and Alq3 was adopted as electron-transporting layer. As shown in Fig. 6, the EL spectra of the devices 1-3 exhibited green emission with maximal peaks at 540 nm, 532 nm, and 528 nm, respectively.

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0.66 lm/W, respectively. These results indicated that the performances of the devices decreased as the molecular length of pyrene functionalized triphenylamines was extended. The possible reason for this phenomenon might be that the compounds with more carbazole-vinylene unit, such as TCCP, would crystallize more easily than TP and TCP, which will be disadvantageous to the electroluminescent properties. Therefore, the EL device 1 based on TP exhibited the best performance among the three devices, suggesting that TP is promising greenemitting material for the preparation of highly efficient lightemitting diodes.

Fig. 6 Normalized electroluminescence (EL) spectra of the devices 1-3 based on ITO/PEDOT:PSS/TP(45 nm)/Alq3 (55 nm)/LiF/Al, (ITO/PEDOT:PSS/TCP(45 nm)/Alq3 (55 nm)/LiF/Al) and (ITO/PEDOT:PSS/TCCP(45 nm)/Alq3 (55 nm)/LiF/Al), respectively.

Fig. 8 Current efficiency and power efficiency-current density of devices 1-3 based on TP, TCP and TCCP. 40

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Fig. 7 L-V-J characteristics of the devices 1-3 based on TP, TCP and TCCP.

The luminance-voltage-current density (L-V-J) characteristics for the EL devices based on TP, TCP, TCCP are shown in Fig. 7, and the device performances are summarized in Table 3. The turn-on voltages of these devices were 2.8 V for TP, 4.4 V for TCP, and 3.3 V for TCCP. The device based on TP showed a maximum luminance of 29880 cd/m2 at 9.5 V. The device based on TCP and TCCP exhibited weak maximum brightness of 13470 cd/m2 at 12.0 V to 7767 cd/m2 at 11.0 V, respectively. The current efficiency and power efficiency versus current density of devices are shown in Fig. 8. Device 1 based on TP showed a maximum current efficiency of 3.34 cd/A and a maximum power efficiency of 2.67 lm/W. Similarly, device 2 and 3 based on TCP and TCCP showed maximum current efficiencies of 1.18 cd/A and 1.00 cd/A, maximum power efficiencies of 0.35 lm/W and 6 | Journal Name, [year], [vol], 00–00

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Conclusions In summary, new pyrene-functionallized triphenylamine derivatives (TP, TCP and TCCP) were synthesized by alternate Heck and Wittig reactions. It was found that the increase of the number of carbazole-vinylene unit as the conjugated bridge resulted in blue-shifts of the absorption and emission maxima in solutions on account of the increasing of the nonplanarity. It should be noted that the introduction of triphenylamine unit could suppress the formation of excimer from pyrene, so that the obtained pyrene derivatives emitted strong green light. Furthermore, compounds TP, TCP and TCCP were employed as the emitters as well as the hole-transporting materials in EL devices based on ITO/PEDOT:PSS/pyrene-functionallized triphenylamine (45 nm)/Alq3 (55 nm)/LiF/Al, in which Alq3 was used as electron-transporting layer. We found that the device 1 based on TP exhibited good performance with a low turn-on voltage of 2.8 V, a high maximum luminance of 29880 cd/m2 at 9.5 V, a high current efficiency of 3.34 cd/A, and a high power efficiency of 2.67 lm/w. It suggested the luminogens of pyrene functionallized triphenylamines may be used as promising materials for the construction of efficient non-doped green OLEDs.

Experimental section Materials and Measurements This journal is © The Royal Society of Chemistry [year]


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H NMR spectra were recorded on a Mercury plus 500 MHz

using CDCl3 as solvent in all cases.

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Devicea λELb (nm) Vonc (V) Lmaxd (cd/m2) ηce (cd/A) ηpf (lm/W) 1 540 2.8 29880 3.34 2.67 2 532 4.4 13470 1.18 0.35 3 518 3.3 7767 1.00 0.66 a Devive 1: ITO/PEDOT/PSS/TP/Alq3/LiF/Al; device 2: ITO/PEDOT/PSS/TCP/Alq3/LiF/Al; device 3: ITO/PEDOT/PSS/TCCP/Alq3/LiF/Al. b Peak electroluminescence. c Turn-on voltage. d Maximum brightness. e Maximum current efficiency. f Maximum power efficiency. 50 treatment in detergent solutions, followed by rinsed with acetone, 13 C NMR spectra were recorded on a Mercury plus 125 MHz boiled in isopropanol, rinsed in methanol, and then in de-ionized using CDCl3 as solvent in all cases. UV-vis absorption spectra water. The glass was dried in vacuum oven between each were determined on a Shimadzu UV-1601PC Spectrophotometer. cleaning step above. To reduce the possibility of electrical shorts Photoluminescence (PL) spectra were carried out on a Shimadzu on the ITO anode and increase the value of its work function, the RF-5301 Luminescence Spectrometer. The fluorescence quantum 55 ITO substrate was treated using a Plasma Cleaner (PDC-32G-2, yields of TP, TCP, TCCP in cyclohexane were determined 100W) with the oxygen ambient. Prior to the deposition, all the against 9,10-diphenylanthracene (Φr = 0.95, in cyclohexane) as a organic materials were further purified by sublimation method. standard excited at 392 nm, and the values were gained according The organic layer was sequentially deposited onto the substrate to the following equation: Φs=Φr⋅Fs/Fr⋅Ar/As⋅(nr/ns)2, where Φ is without breaking vacuum at a pressure of about 10-4 Pa. A very the fluorescence quantum yield, A is the absorbance of the 60 thin layer of LiF could enhance electron injection from aluminum solution, F is the integral area of the emission peak, n is the cathode. A shadows mask with 2 × 3 mm2 openings was used to refractive index of the solution, and the subscripts of “s” and “r” define the cathodes. The EL spectrum, brightness and the currentrefer to the solutions of the sample and reference, respectively. IR brightness-voltage characteristics of the devices were measured spectra were measured using a Germany bruker vertex 80v FT-IR with a rapid scan system using a spectrophotometer (PR-650, spectrameter by incorporating samples in KBr disks. Mass 65 Photo Research) and a computer-controlled, programmable, spectra were performed on Agilent 1100 MS series and AXIMA direct-current (DC) source (Keithley 2400). Luminance-voltage CFR MALDI/TOF (Matrix assisted laser desorption and current-voltage characteristics were measured at room ionization/Time-of-flight) MS (COMPACT). C, H and N temperature under an ambient atmosphere. Elemental analyses were taken on a Perkin-Elmer 240C Synthetic procedures and characterizations elemental analyzer. Cyclic voltammetry (CV) was performed using CHI 604B electrochemical working station and 70 Compounds (4-bromobenzyl)triphenylphosphonium bromide, 6measurements were carried out in CH2Cl2 containing 0.1 M iodo-9-octyl-9H-carbazole-3-carbaldehyde, 4-(N,Ntetrabutylammonium hexafluorophosphate (Bu4NPF6) as a diphenylamino) benzaldehyde, N-phenyl-N-(4supporting electrolyte at room temperature. Platinum button was vinylphenyl)benzenamine and 1-vinylpyrene were synthesized used as a working electrode and a platinum wire as a counter according to the reported procedures.18,28 electrode, and all potentials were recorded versus Ag/AgCl (saturated) as a reference electrode. The scan rate was maintained 75 (E)-4-(4-Bromostyryl)-N,N-diphenylaniline (1) A mixture of 4at 100 mV/s. Differential scanning calorimetric (DSC) (N,N-diphenylamino)benzaldehyde (2.73 g, 0.01 mol) and (4measurements were performed on a NETZSCH DSC204 bromobenzyl)triphenylphosphonium bromide (1.87 g, 0.012 mol) instrument. Thermogravimetric analyses (TGA) were performed was suspended in absolute THF (40 mL), and t-BuOK (1.68 g, on a TA Q500 thermogravimeter. The thermal stability of the 0.015 mol) in THF was added dropwise with stirring at 0 °C . samples under nitrogen atmosphere was determined by 80 The mixture was stirred at room temperature for 4 h, and then measuring their weight loss, heated at a rate of 10 °C/min from was poured into 300 mL water with stirring. The mixture was 25 °C to 600 °C. Tetrahydronfuran (THF) was distilled over extracted with CH2Cl2 (3 × 50 mL), and the organic phase was sodium and benzophenone. DMF was distilled from phosphorous combined to wash with brine. After dried with anhydrous pentoxide, and other chemicals were used as received without MgSO4, the solvent was removed. The crude product was further purification. 85 purified by column chromatogram (silica gel) with petroleum Theoretical calculation methods ether/dichloromethane (v/v = 10/1) as an eluent, followed by recrystallization in a mixture of petroleum ether and The geometrical structures of TP, TCP and TCCP were dichloromethane to give a pale green solid in a yield of 78 %. optimized by employing the density functional theory at the Mp: 180.0-182.0 °C. 1H NMR (500 MHz, TMS, CDCl3): δ = B3LYP/6-31G (d) level with the Gaussian 03W program 90 7.45 (d, J = 8.5 Hz, 2H), 7.38-7.34 (m, 4H), 7.28 (s, 1H), 7.26 (s, package.29 Molecular orbitals were visualized using Gaussview. 2H), 7.25 (s, 1H), 7.11 (d, J = 7.5 Hz, 4H), 7.04 (d, J = 8.5 Hz, Fabrication of the OLEDs and EL measurements 4H), 7.02 (s, 1H), 6.91(d, J = 16.5 Hz, 1H) (Fig. S3) IR (KBr, cm–1): 2920, 2850, 1380, 1110, 958, 694. Elemental analysis The devices were grown on a glass, which was pre-coated with calculated for C26H20BrN: C, 73.24; H, 4.73; N, 3.29. Found: C, indium tin oxide (ITO) having a sheet resistance equal to 20 Ω 95 73.16, H, 4.75, N, 3.35. MS, m/z: calcd: 426.4, found: 426.0 (Fig. cm-2. The ITO glass was routinely cleaned by ultrasonic S4). This journal is © The Royal Society of Chemistry [year]

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Table 3. EL performance of devices 1-3.



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(E)-7-(4-(Diphenylamino)styryl)-9-octyl-9H-carbazole-3carbaldehyde (2) A mixture of compound N-phenyl-N-(4vinylphenyl)benzenamine (3.25 g 0.012 mol), 6-iodo-9-octyl-9Hcarbazole-3-carbaldehyde (4.33 g, 0.01 mol), anhydrous potassium carbonate (2.76 g, 0.02 mol), tetrabutylammonium bromide (3.22 g, 0.01 mol) and Pd(OAc)2 (20 mg, 0.089 mmol) was added into 20 mL anhydrous DMF under N2 atmosphere. The mixture was stirred at 110 °C for 12 h, and then was cooled to room temperature, followed by poured into 300 mL water with stirring. After extraction with CH2Cl2 (3 × 50 mL), the organic phase was combined and washed with brine. After dried with anhydrous MgSO4, the solvent was removed. The crude product was purified by column chromatogram (silica gel) with petroleum ether/dichloromethane (v/v = 1/1) as eluent, and then recrystallized in a mixture of tetrahydrofuran and ethanol to give a yellow-green solid in a yield of 72%. Mp: 146.0-148.0 °C. 1H NMR (500 MHz, TMS, CDCl3) δ = 10.09 (s, 1H), 8.62 (d, J = 1.5 Hz, 1H), 8.25 (d, J = 1.5 Hz, 1H), 8.00 (dd, J = 8.5, 1.5 Hz, 1H), 7.69 (dd, J = 8.5, 1.5 Hz, 1H), 7.46-7.40 (m, 4H), 7.28-7.27 (m, 4H), 7.20 (d, J = 16.5 Hz, 1H), 7.14-7.10 (m, 5H), 7.09-7.08 (d, J = 8.5 Hz, 2H), 7.03 (t, J = 7.5 Hz, 2H), 4.31 (t, J = 7.5 Hz, 2H), 1.91-1.83(m, 2H), 1.40-1.22 (m, 10H), 0.86 (t, J = 7.0 Hz, 3H) (Fig. S5). IR (KBr, cm–1): 2920, 2850, 1680, 1590, 1380, 1110, 962, 812, 694. Elemental analysis calculated for C41H40N2O: C, 85.38; H, 6.99; N, 4.86. Found: C, 85.27, H, 7.02, N, 4.93. MS, m/z: calcd: 576.8, found: 576.9 (Fig. S6). 4-((E)-2-(6-((E)-4-Bromostyryl)-9-octyl-9H-carbazol-2yl)vinyl)-N,N-diphenyl-aniline (3) According to the synthetic procedure of compound 1, compound 3 as a pale green solid was prepared from 2 and (4-bromobenzyl)triphenylphosphonium bromide in a yield of 52 %. mp: 194.0-196.0 °C. 1H NMR (500 MHz, TMS, CDCl3): δ = 8.23 (dd, J = 9.5, 1.0 Hz, 2H), 7.66-7.63 (m, 2H), 7.48 (d, J = 8.5 Hz, 2H), 7.45-7.41 (m, 4H), 7.36 (d, J = 8.5 Hz, 2H), 7.30 (d, J = 16.0 Hz, 2H), 7.27(s, 2H), 7.25 (s, 1H), 7.22(d, J = 16.0 Hz, 1H), 7.14-7.12 (m, 5H), 7.10-7.08 (m, 3H), 7.06 (d, J = 10.0 Hz, 1H), 7.02 (d, J = 7.5 Hz, 1H), 4.28 (t, J = 7.5 Hz, 2H), 1.91-1.85 (m, 2H), 1.38-1.23 (m, 10H), 0.86 (t, J = 7.0 Hz, 3H) (Fig. S7). IR (KBr, cm–1): 2920, 2850, 1380, 1110, 960, 692. Elemental analysis calculated for C48H45BrN2: C, 79.00; H, 6.22; N, 3.84. Found: C, 78.92, H, 6.26, N, 3.86. MS, m/z: calcd: 729.8, found: 729.8 (Fig. S8). (E)-4-(2-(9-Octyl-6-vinyl-9H-carbazol-2-yl)vinyl)-N,Ndiphenylaniline (4) Potassium tert-butoxide 1.12 g (10.0 mmol) was added to a solution of triphenylmetrylphosphonium iodine (4.85 g, 12.0 mmol) in 30 mL dry THF at 0 °C. After the mixture was stirred for 15 min at room temperature, 5.77 g (10.0 mmol) (E)-7-(4-(diphenylamino)styryl)-9-octyl-9H-carbazole-3carbaldehyde (2) was added at 0 °C. After stirred at room temperature for another 2 h, the mixture was poured into 300 mL water with stirring. The mixture was extracted with CH2Cl2 (3 × 50 mL), the organic phase was combined and washed with brine. After dried with anhydrous MgSO4, the solvent was removed. The crude product was purified by column chromatogram (silica gel) with petroleum ether/dichloromethane (v/v = 4/1) as eluent, and then recrystallized in a mixture of petroleum ether and dichloromethane to give a green solid in a yield of 65%. Mp: 90.0-92.0 °C. 1H NMR (500 MHz, TMS, CDCl3) δ = 8.24 (s, 1H), 8.09 (s, 1H), 7.67 (dd, J = 8.5, 1.5 Hz, 1H), 7.47 (d, J = 8.5 Hz,


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3H), 7.40-7.38 (m, 2H), 7.31-7.30 (m, 3H), 7.28 (s, 1H), 7.23 (s, 1H), 7.16 (d, J = 7.5 Hz, 5H), 7.11 (d, J = 8.5 Hz, 2H), 7.06 (t, J = 7.5 Hz, 2H), 6.98-6.92 (m, 1H), 5.81 (d, J = 17.5 Hz, 1H), 5.24 (d, J = 11.0 Hz, 1H), 4.30 (t, J = 7.5 Hz, 2H), 1.93-1.87(m, 2H), 1.29-1.25 (m, 10H), 0.90 (t, J = 7.0 Hz, 3H) (Fig. S9). IR (KBr, cm-1): 2920, 2850, 1510, 1380, 1280, 1110, 960, 812, 694. Elemental analysis calculated forC42H42N2: C, 87.76; H, 7.36; N, 4.87. Found: C, 87.69, H, 7.38, N, 4.93. MS, m/z: calcd: 574.8, found: 574.3 (Fig. S10). 6-((E)-2-(7-((E)-4-(Diphenylamino)styryl)-9-octyl-9Hcarbazol-3-yl)vinyl)-9-octyl-9H-carbazole-3-carbaldehyde (5) According to the synthetic procedure of compound 2, compound 5 was prepared from 4 and 6-iodo-9-octyl-9H-carbazole-3carbaldehyde in a yield of 60 % as a yellow-green solid. Mp: 116.0-118.0 °C. 1H NMR (500 MHz, TMS, CDCl3) δ = 10.11 (s, 1H), 8.64 (d, J = 1.5 Hz, 1H), 8.32 (d, J = 1.5 Hz, 1H), 8.29 (d, J = 1.5 Hz, 1H), 8.24 (d, J = 1.5 Hz, 1H), 8.01 (dd, J = 8.5, 1.5 Hz, 1H), 7.77 (dd, J = 8.5 Hz, 1.5 Hz, 1H), 7.71 (dd, J = 8.5 Hz, 2.0 Hz, 1H), 7.65 (dd, J = 8.5 Hz, 1.5 Hz, 1H), 7.47-7.43 (m, 4H), 7.40 (d, J = 7.0 Hz, 1H), 7.37 (d, J = 4.5 Hz, 3H), 7.34 (d, J = 8.5 Hz, 1H), 7.29-7.27 (m, 3H), 7.21 (s, 1H), 7.14-7.08 (m, 7H), 7.05-7.02 (m, 2H), 4.34-4.27 (m, 4H), 1.93-1.85(m, 4H), 1.281.23 (m, 20H), 0.88-0.85 (m, 6H) (Fig. S11). IR (KBr, cm-1): 2920, 2850, 1640, 1380, 1120, 960, 802. Elemental analysis calculated forC63H65N3O: C, 85.97; H, 7.44; N, 4.77. Found: C, 85.89, H, 7.46, N, 4.82. MS, m/z: calcd: 880.2, found: 880.4 (Fig. S12). 4-((E)-2-(6-((E)-2-(6-((E)-4-Bromostyryl)-9-octyl-9Hcarbazol-3-yl)vinyl)-9-octyl-9H-carbazol-2-yl)vinyl)-N,Ndiphenylaniline (6) According to the synthetic procedure of compound 1, compound 6 was prepared from 5 and (4bromobenzyl)triphenylphosphonium bromide in a yield of 40 % as a yellow solid. Mp: 94.0-96.0 °C. 1H NMR (500 MHz, TMS, CDCl3): δ = 8.30 (s, 2H), 8.26 (d, J = 6.0 Hz, 2H), 7.73-7.71 (m, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.49 (d, J = 8.5 Hz, 2H), 7.47 (s, 1H), 7.45-7.42 (m, 3H), 7.40 (s, 1H), 7.38-7.34 (m, 6H), 7.32 (d, J = 16.0 Hz, 1H), 7.29(s, 1H), 7.27 (s, 2H), 7.22(s, 1H), 7.14 (d, J = 7.5 Hz, 5H), 7.10 (d, J = 3.5 Hz, 2H), 7.09 (s, 1H), 7.06 (d, J = 14.0 Hz, 1H), 7.03 (d, J = 7.5 Hz, 1H), 4.31-4.28 (m, 4H), 1.921.86 (m, 4H), 1.40-1.23 (m, 20H), 0.87 (t, J = 7.0 Hz, 6H) (Fig. S13). IR (KBr, cm-1): 2920, 2850, 1720, 1640, 1380, 1110, 958, 698. Elemental analysis calculated for C70H70BrN3: C, 81.37; H, 6.83; N, 4.07. Found: C, 81.26, H, 6.78, N, 4.13. MS, m/z: calcd: 1033.2, found: 1033.4 (Fig. S14). N,N-Diphenyl-4-((E)-4-((E)-2-(pyren-2-yl)vinyl)styryl)aniline (TP) A mixture of 1 (4.26 g, 10.0 mmol)), 1-vinylpyrene (2.74 g, 12.00 mmol), anhydrouspotassium carbonate (2.76 g, 20.00 mmol), tetrabutylammonium bromide (3.22 g, 10.00 mmol), and Pd(OAc)2 (20 mg, 0.089 mmol) was added into 30 mL anhydrous DMF under N2 atmosphere. The mixture was stirred at 110 °C 12 h, and then was cooled to room temperature, followed by poured into 300 mL water with stirring. The solid was collected by filtration. The crude product was purified by column chromatogram (silica gel) with petroleum ether/dichloromethane (v/v = 3/1) as eluent, and then recrystallized in a mixture of petroleum ether and dichloromethane to give a light yellow solid in a yield of 65%. Mp: 214.0-216.0 °C. 1H NMR (500 MHz, TMS, CDCl3) δ = 8.50 (d, J = 9.0 Hz, 1H), 8.32 (d, J = 8.0 Hz, This journal is © The Royal Society of Chemistry [year]


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C, 89.53; H, 6.92; N, 3.56. Found: C, 89.46; H, 6.90, N, 3.61. MS, m/z: calcd: 1180.6, found: 1180.7 (Fig. S23).

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This work was financially supported by the National Natural Science Foundation of China (51073068), the 973 Program (2009CB939701), the Open Project of the State Key Laboratory of Supramolecular Structure and Materials (SKLSSM201203).

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State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China. E-mail: [email protected], [email protected]; Fax: +86-43188923907; Tel: +86-431-88499179 † Electronic Supplementary Information (ESI) available: fluorescence spectra; 1H NMR, 13C NMR, and MALDI/TOF MS spectra of new compounds. See DOI: 10.1039/b000000x/ 1. (a) T. M. Figueira-Duarte and K. Müllen, Chem. Rev., 2011, 111, 7260-7314; (b) E. Holder, B. M. W. Langeveld and U. S. Schubert, Adv. Mater., 2005, 17, 1109-1121; (c) H. J. Bolink, E. Barea, R. D. Costa, S. Sudhakar, C. Zhen and A. Sellinger, Org. Electron., 2008, 9, 155-163; (d) C. W. Tang and S. A. Vanslyke, Appl. Phys. Lett., 1987, 51, 913-915; (e) J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns and A. B. Holmes, Nature., 1990, 347, 539-541. 2. M. D. McGehee and A. J. Heeger, Adv. Mater., 2000, 12, 1655-1668. 3. (a) A. R. Murphy and J. M. J. Fréchet, Chem. Rev., 2007, 107, 10661096; (b) B. Crone, A. Dodabalapur, A. Gelperin, L. Torsi, H. E. Katz, A. J. Lovinger and Z. Bao, Appl. Phys. Lett., 2001, 78, 22292231; (c) T. Someya, H. E. Katz, A. Gelperin, A. J. Lovinger and A. Dodabalapur, Appl. Phys. Lett., 2002, 81, 3079-3081. 4. (a) T. Kowada, J. Kituta, A. Kubo, M. Ishii, H. Maeda, S. Mizukami and K. Kikuchi, J. Am. Chem. Soc., 2011, 133, 17772-17776; (b) S. Yao, H.-Y. Ahn, X. H. Wang, J. Fu, E. W. V. Stryland, D. J. Hagan and K. D. Belfield, J. Org. Chem., 2010, 75, 3965-3974; (c) N. Fu, Y. J. Xiong and T. C. Squier, J. Am. Chem. Soc., 2012, 134, 1853018533. 5. (a) Y. L. Wang, T. L. Liu, L. Y. Bu, J. F. Li, C. Yang, X. J. Li, Y. Tao and W. J. Yang, J. Phys. Chem., 2012, 116, 15576-15583; (b) Y.-J. Cheng, J. D. Luo, S. Hau, D. H. Bale, T.-D. Kim, Z. W. Shi, D. B. Lao, N. M. Tucker, Y. Q. Tian, L. R. Dalton, P. J. Reid and A. K.-Y. Jen, Chem. Mater., 2007, 19, 1154-1163; (c) D. J. Armitt and G. T. Crisp, J. Org. Chem., 2006, 71, 3417-3422. 6. (a) B. W. D’Andrade and S. R. Forrest, Adv. Mater., 2004, 16, 15851595; (b) C.-T. Chen, Chem. Mater., 2004, 16, 4389-4400; (c) P.-I. Shih, Y.-H. Tseng, F.-I. Wu, A. K. Dixit and C.-F. Shu, Adv. Funct. Mater., 2006, 16, 1582-1589. 7. J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. MacKay, R. H. Friend, P. L. Burn and A. B. Holmes, Nature., 1990, 347, 539-541. 8. (a) M. Fabrice, V.-A. Christine, A. Jörg, R. Pascal and B. Hugues, F. Frédéric, J. Mater. Chem., 2006, 16, 2380-2386; (b) J. C. Kwon, J.-P. Hong, S. Noh, T.-M. Kim, J.-J. Kim, C. H. Lee, S. H. Lee and J.-I. Hong, New. J. Chem., 2012, 36, 1813-1818. 9. (a) Y. Jiang, L. Wang, Y. Zhou, Y. X. Cui, J. Wang, Y. Cao and J. Pei, Chem. Asian. J., 2009, 4, 548-553; (b) M. Halim, J. N. G. Pillow, I. D. W. Samuel and P. L. Burn, Adv. Mater., 1999, 11, 371-374; (c) P. J. M. Jonathan, B. N. Ebinazar, D. A. Thomas and D. W. S. Ifor, Appl. Phys. Lett., 2004, 85, 1463-1465. 10. Z. F. Chang, S. H. Ye, B. R. He, Z. R. Bei, L. Y. Lin, P. Lu, B. Chen, Z. J. Zhao and H. Y. Qiu, Chem. Asian. J., 2013, 8, 444-449. 11. (a) Z. J. Zhao, X. J. Xu, H. B. Wang, P. Lu, G. Yu and Y. Q. Liu, J. Org. Chem., 2008, 73, 594-602; (b) Z. J. Zhao, J.-H. Li, X. P. Chen, X. M. Wang, P. Lu and Y. Yang, J. Org. Chem., 2009, 74, 383-395; (c) S.-L. Lai, Q.-X. Tong, M.-Y. Chan, T.-W. Ng, M.-F. Lo, S.-T. Lee and C.-S. Lee, J. Mater. Chem., 2011, 21, 1206-1211. 12. S. Tao, Z. Peng, X. Zhang, P. Wang and C. S. Lee, Adv. Funct.

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1H), 8.22-8.15 (m, 4H), 8.13 (d, J = 9.0 Hz, 1H), 8.05 (s, 2H), 8.00 (t, J = 7.5 Hz, 1H), 7.66 (d, J =8.0 Hz, 2H), 7.55 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 8.5 Hz, 2H), 7.35 (d, J = 16.0 Hz, 1H), 7.29(s, 1H), 7.27 (s, 2H), 7.25 (s, 1H), 7.12 (t, J = 8.0 Hz, 5H), 7.08-7.02 (m, 5H) (Fig. S15). 13C NMR (125 MHz, CDCl3) δ (ppm) = 147.56, 147.47, 137.29, 136.80, 132.00, 132.59, 131.47, 131.00, 130.89, 129.32, 128.44, 128.26, 127.63, 127.51, 127.42, 127.30, 127.08, 126.76, 126.63, 126.03, 125.33, 125.19, 125.06, 125.03, 124.57, 123.63, 123.56, 123.10, 123.06 (Fig. S16). IR (KBr, cm-1): 2920, 2860, 1650, 1380, 1110, 960, 840. Elemental analysis calculated forC44H31N: C, 92.11; H, 5.45; N, 2.44. Found: C, 92.02, H, 5.48, N, 2.47. MS, m/z: calcd: 573.7, found: 573.2 (Fig. S17). 4-((E)-2-(9-Octyl-6-((E)-4-((E)-2-(pyren-2-yl)vinyl)styryl)-9Hcarbazol-2-yl)vinyl)-N,N-diphenylaniline (TCP) According to the synthetic procedure of compound TP, compound TCP was prepared from 3 and 1-vinylpyrene in a yield of 62 % as a light yellow solid. Mp: 234.0-236.0 °C. 1H NMR (500 MHz, TMS, CDCl3) δ = 8.53 (d, J = 9.5 Hz, 1H), 8.35 (d, J = 8.0 Hz, 1H), 8.29 (s, 1H), 8.24 (s, 2H), 8.21-8.14 (m, 5H), 8.06 (s, 2H), 8.00 (t, J = 7.5 Hz, 1H), 7.71-7.69 (m, 3H), 7.64 (t, J = 9.0 Hz, 3H), 7.45 (d, J = 8.5 Hz, 2H), 7.41-7.36 (m, 4H), 7.28 (d, J = 8.0 Hz, 3H), 7.21 (d, J = 16.0 Hz, 2H), 7.14 (d, J = 8.0 Hz, 5H), 7.09 (d, J = 8.0 Hz, 2H), 7.03 (t, J = 7.5 Hz, 2H) 4.29 (t, J = 7.0 Hz, 2H), 1.91-1.86 (m, 2H), 1.35-1.23 (m, 10H), 0.87 (t, J = 7.0 Hz, 3H) (Fig. S18). 13C NMR (125 MHz, CDCl3) δ (ppm) = 147.71, 146.87, 140.70, 140.50, 137.65, 136.55, 132.39, 132.06, 131.60, 131.55, 131.02, 130.85, 129.71, 129.29, 129.12, 128.74, 128.42, 128.08, 127.60, 127.51, 127.26, 127.14, 127.08, 126.68, 126.01, 125.73, 125.29, 125.19, 125.14, 125.05, 124.72, 124.59, 124.38, 123.99, 123.62, 123.34, 123.31, 123.09, 122.89, 118.78, 118.44, 109.11, 43.34, 31.82, 29.39, 29.20, 29.07, 27.32, 22.64, 14.10 (Fig. S19). IR (KBr, cm-1): 2920, 2850, 1590, 1380, 1110, 957, 802, 694. Elemental analysis calculated for C66H56N2: C, 90.37; H, 6.43; N, 3.19. Found: C, 90.26, H, 6.46, N, 3.23. MS, m/z: calcd: 877.2, found: 876.6 (Fig. S20). 4-((E)-2-(9-Octyl-6-((E)-2-(9-octyl-6-((E)-4-((E)-2-(pyren-2yl)vinyl)styryl)-9H-carbazol-3-yl)vinyl)-9H-carbazol-2yl)vinyl)-N,N-diphenylaniline (TCCP) According to the synthetic procedure of compound TP, compound TCCP was prepared from 6 and 1-vinylpyrene in a yield of 54 % as a light yellow solid. Mp: 159.0-161.0 °C. 1H NMR (500 MHz, TMS, CDCl3) δ = 8.56 (d, J = 9.5 Hz, 1H), 8.38 (d, J = 8.5 Hz, 1H), 8.34 (d, J = 2.0 Hz, 3H), 8.28 (d, J = 9.5 Hz, 1H), 8.24-8.17 (m, 5H), 8.09 (s, 2H), 8.04 (t, J = 7.5 Hz, 1H), 7.71-7.73 (m, 5H), 7.69-7.67 (m, 3H), 7.49 (d, J = 8.5 Hz, 2H), 7.45-7.39 (m, 8H), 7.30 (d, J = 8.5 Hz, 3H), 7.28-7.24 (m, 3H), 7.17-7.12 (m, 7H), 7.05 (t, J = 7.5 Hz, 2H), 4.33 (t, J = 6.5 Hz, 4H), 1.95-1.91 (m, 4H), 1.39-1.26 (m, 20H), 0.92-0.89 (m, 6H) (Fig. S21). 13C NMR (125 MHz, CDCl3) δ (ppm) = 147.73, 146.84, 140.70, 140.51, 140.38, 137.67, 136.50, 132.49, 132.06, 131.60, 131.52, 131.03, 130.82, 129.76, 129.51, 129.41, 129.29, 128.96, 128.66, 128.40, 128.21, 127.57, 127.52, 127.24, 127.15, 127.10, 126.68, 126.00, 125.64, 125.59, 125.28, 125.19, 125.05, 124.69, 124.55, 124.50, 124.37, 124.04, 123.59, 123.40, 123.35, 123.10, 122.88, 118.78, 118.45, 118.32, 109.08, 109.03, 43.31, 31.85, 29.42, 29.24, 29.10, 27.35, 22.66, 14.13 (Fig. S22). IR (KBr, cm-1): 2920, 2850, 1640, 1380, 1110, 962, 694. Elemental analysis calculated forC88H81N3:



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Page 11 of 11 Organic & Biomolecular Chemistry DOI: 10.1039/C3OB41185K

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