Compound and organic electronic device using the same

Abstract

A novel compound is disclosed, which comprises: a 7-membered ring segment, which is formed by a cis-stilbene segment and a bridge atom with four bonds; and a fluorene segment connecting to the bridge atom with a double bond. In addition, an organic electronic device is also disclosed, and an organic layer therein comprises the novel compound of the present invention.

Claims

1. A compound represented by the following formula (I-1) or (I-3): ##STR00018## wherein R.sub.1 is aryl, heteroaryl, or P(?O)R.sub.3R.sub.4; wherein R.sub.2 is halogen, aryl, heteroaryl, or P(?O)R.sub.3R.sub.4; wherein each of R.sub.3 and R.sub.4 independently is H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.20 cycloalkyl, C.sub.3-C.sub.20 heterocycloalkyl, NR.sub.aR.sub.b, aryl, or heteroaryl, in which each of R.sub.a and R.sub.b independently is H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.20 cycloalkyl, C.sub.3-C.sub.20 heterocycloalkyl, aryl, or heteroaryl.

2. The compound of claim 1, wherein R.sub.1 is substituted aryl, substituted heteroaryl, or P(?O)R.sub.3R.sub.4.

3. The compound of claim 2, wherein R.sub.1 is ##STR00019## substituted heteroaryl, or P(?O)R.sub.3R.sub.4; in which R.sub.3 and R.sub.4 are phenyl, 4-cyanophenyl or 4-pyridyl, and X is halogen or CN.

4. The compound of claim 3, wherein R.sub.1 is ##STR00020## or P(?O)R.sub.3R.sub.4, in which R.sub.3 and R.sub.4 are phenyl.

5. The compound of claim 1, wherein R.sub.2 is Br, F, ##STR00021## or P(?O)R.sub.3R.sub.4; in which R.sub.3 and R.sub.4 are phenyl, 4-cyanophenyl or 4-pyridyl, and X is halogen or CN.

6. The compound of claim 5, wherein R.sub.2 is F, ##STR00022## or P(?O)R.sub.3R.sub.4, in which R.sub.3 and R.sub.4 are phenyl.

7. The compound of claim 1, which has glass transition temperatures (T.sub.g) ranging from 127? C. to 162? C., decomposition temperatures (T.sub.d) ranging from 350? C. to 436? C., oxidation potentials ranging from 1.01 V to 1.16 V, reduction potentials ranging from ?1.91 V to ?2.29 V, highest occupied molecular orbital energy levels (E.sub.HOMO) ranging from 5.95 eV to 6.19 eV and/or lowest unoccupied molecular orbital energy levels (E.sub.LUMO) ranging from 2.67 eV to 2.96 eV.

8. The compound of claim 1, which is represented by any one of the following formulas (III-1), (III-3), (IV-1), and (IV-3): ##STR00023##

9. The compound of claim 1, which is applied in an organic light emitting diode (OLED) as hole-blocking materials, electron-transporting materials or light-emitting materials.

10. An organic electronic device, comprising: a first electrode; a second electrode; and an organic layer disposed between the first electrode and the second electrode, and comprising a compound represented by following formula (I-1) or (I-3): ##STR00024## wherein R.sub.1 is aryl, heteroaryl, or P(?O)R.sub.3R.sub.4; wherein R.sub.2 is halogen, aryl, heteroaryl, or P(?O)R.sub.3R.sub.4; wherein each of R.sub.3 and R.sub.4 independently is H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.20 cycloalkyl, C.sub.3-C.sub.20 heterocycloalkyl, NR.sub.aR.sub.b, aryl, or heteroaryl, in which each of R.sub.a and R.sub.b independently is H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.20 cycloalkyl, C.sub.3-C.sub.20 heterocycloalkyl, aryl, or heteroaryl.

11. The organic electronic device of claim 10, wherein the organic electronic device is an organic light emitting device, and the organic layer is an electron transport layer or a hole blocking layer.

12. The organic electronic device of claim 10, wherein the organic electronic device is an organic solar cell device, and the organic layer is a carrier transport layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a perspective view showing an OLED device of the prior art;

(2) FIG. 2 is a perspective view showing an OLED device of the present invention; and

(3) FIG. 3 is a perspective view showing an organic solar cell device of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

(4) The present invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of description rather than of limitation. Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

Example 1Preparation of Compound of Formula (II-1)

(5) ##STR00013##

(6) The compound of the formula (II-1) was prepared by using the following steps.

(7) 7.0 mmol of fluorene was dissolved in 20 mL of anhydrous tetrahydrofuran (THF), and the obtained solution was stirred in an environment of 0? C. 5.0 mL of H-butyllithium hexanes solution (8 mmol) from a n-butyllithium solution 1.6 M is hexanes was added dropwise info the solution containing fluorene and the obtained solution was stirred for 30 min. Then, 8.4 mmol of neat trimethylsilyl chloride (1 mL) was added thereto, followed by stirring for 3 hours. The reaction mixture was quenched with, saturated aqueous ammonium chloride (15 mL) and the aqueous layer was extracted with CH.sub.2Cl.sub.2 (3?20 mL). The organic extracts with sodium sulfate (5 grams) were dried and then concentrated to get the 5-trimethylsilyl-fluorene.

(8) Next, 120 mg of 5-trimethylsilyl-fluorene (0.5 mmol) was dissolved in 7 mL of anhydrous THE, and the reaction flask was cooled to ?78? C. 0.3 mL of H-butyllithium in hexanes solution (0.5 mmol) from a n-butyllithium solution 1.5 M in hexanes was then added dropwise into the solution containing 5-trimethylsilyl-fluorene, and the obtained solution was stirred for 30 min. 120 mg of 3,7-dibromo-dibenzosuberenone (0.5 mmol) dissolved in 5 mL of anhydrous THF was dropwise added into the reaction mixture at 0? C. and then the reaction mixture was warmed to ambient temperature and stirred for 24 hours. After 24 hours, 2 mL of water was added into the reaction mixture for executing a quenching reaction, and then THF was removed by rotary evaporation. The product was extracted by using dichloromethane to obtain an extract liquid extract. Then, 1 g magnesium sulfate was added into the extract liquid extract, and the extract liquid extract was sequentially treated with a drying process, a filtering process and a rotary evaporating process to obtain an intermediate product. The intermediate product was then purified by column chromatography (CH.sub.2Cl.sub.2/hexanes: 1/5) to obtain clear crystal white solid represented fey the formula (II-1).

(9) Data fertile compound of the formula (II-1): M.W.: 512.23; .sup.1H NMR (400 MHz, CDCl.sub.3) ? 7.75 (d, J=1.8, 2H), 7.66 (d, J=7.4 Hz, 2H), 7.59 (dd, J=8.1, 2.1 Hz, 2H), 7.39 (t, J=8.2 Hz, 2H), 7.27 (t, J=7.4 Hz, 2H), 7.00 (t, J=7.6 Hz, 2H), 6.97 (s, 2H), 6.51 (d, J=7.9 Hz, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) ? 140.83, 138.90, 137.28, 137.16, 133.65, 132.58, 130.66, 130.30, 129,98, 128.37, 126.78, 124.93, 122.86, 119.41; TLC R.sub.f 0.42 CH.sub.2Cl.sub.2/hexanes, 1/5); HRMS calcd for C.sub.28H.sub.16Br.sub.2: 509.9619, found: 509.9627.

Example 2Preparation of Compound of Formulas (II-2) and (II-3)

(10) ##STR00014##

(11) The compounds of the formulas (II-2) and (II-3) were prepared by using the following steps.

(12) 5.0 mmol of 2,7- or 3,6-dibromo-9H-fluoren-9-one (1.69 g) was dissolved in 100 mL of anhydrous tetrahydrofuran (THF), and then 2.5 mL of aqueous hydrazine (64% in water) was added thereto. The obtained solution was placed in an environment of 110? C. for refluxing for 8 hours and then concentrated. Next, 96 mmol of oven-dried MnO.sub.2 (8.24 g) was added into the reaction solution, and the obtained mixture was stirred for 48 hours at ambient temperature and then concentrated to give a red solid. 4.0 mmol of dibenzosuberen-1-thione (894 mg) was added into the solution with the dissolved red solid in 80 mL of anhydrous toluene to obtain a reaction mixture. After stilling the reaction mixture at 80? C. for 2 hours, the reaction mixture was treated with 5 mmol of triphenylphosphine (1.31 g), followed by refluxing for 1 hour and then cooling to ambient temperature. After filtering off the solid and washing the solid with a solution of hexane/acetone (1/1), an orange solid was obtained which is represented by the formulas (II-2) or (II-3).

(13) Data, for the compound of the formula (II-2): M.W.: 512.23; .sup.1H NMR (400 MHz, CDCl.sub.3) ? 7.56 (t, J=6.6 Hz, 2H), 7.55 (d, J=6.4 Hz, 2H), 7.51 (dd, J=6.5, 1.0 Hz, 2H), 7.50 (td, J=6.7, 1.8 Hz, 2H), 7.46 (d, J=8.1 Hz, 2H), 7.34 (dd, J=8.1, 1.6 Hz, 2H), 7.05 (s, 2H), 6.51 (s, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) ? 142.83, 141.12, 137.38, 136.76, 133.37, 131.01, 130.75, 129.88, 128.69, 128.56, 127.73, 126.58, 126.42, 122.59, 122.11; TLC R.sub.f0.4 (Dichloromethane/hexanes, 1/9); HRMS calcd for C.sub.28H.sub.16Br.sub.2: 509.9619, found: 509.9615.

(14) Data for the compound of the formula (II-3): M.W.: 512.23; .sup.1H NMR (400 MHz, CDCl.sub.3) ? 7.73 (d, J=1.9 Hz, 2H), 7.53 (dd, J=7.1, 1.4 Hz, 4H), 7.45 (m, 4H), 7.05 (dd, J=8.6, 1.9 Hz, 2H), 7.03 (s, 2H), 6.29 (d, J=8.5 Hz, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) ? 144.07, 138.36, 138.37, 136.91, 133.32, 130.95, 130.74, 130.70, 128,75, 128.69, 128.42, 127.94, 126.54, 120.65, 120.41; TLC R.sub.f0.4 (Dichloromethane/hexanes, 1/9): HRMS calcd for C.sub.28H.sub.16Br.sub.2: 509.9619, found: 509.9615.

Example 3Preparation of Compound of Formulas (III-1) to (III-3)

(15) ##STR00015##

(16) The compounds of the formulas (III-1) to (III-3) were prepared by using the following steps.

(17) The compounds of formulas (II-1) to (II-3) were treated with a lithiation process by using n-butyllithium (1.5 equiv) in anhydrous THF (200 mL) at ?78? C. The reaction mixtures were then reacted with chlorodiphenylphosphine (2 equiv) for 2 hours, quenched with water (5 mL), extracted with CH.sub.2Cl.sub.2 (3?10 mL), and then concentrated. Next, the reaction mixtures were oxidized with 1 mL of aqueous H.sub.2O.sub.2 (35%). After stirring the reaction mixtures for 3 hours, the resulting white solid was rescrystallized from a solution of CH.sub.2Cl.sub.2 and ethyl acetate to obtain needle white products having the formulas (III-1) to (III-3).

(18) Data for the compound of the formula (III-1): T.sub.m 271? C. M.W.: 754.79; .sup.1H NMR (400 MHz, CDCl.sub.3) ? 7.87 (ddd, J=11.5, 8.0, 1.6 Hz, 2H), 7.78 (dd, J=11.8, 1.4 Hz, 2H), 7.66 (m, 10H), 7.56 (d, J=1.6 Hz, 2H), 7.52 (dd, J=7.7, 1.6 Hz, 2H), 7.48 (dd, J=7.6, 1.4 Hz, 2H), 7.40 (m, 8H), 7.19 (td, J=7.4, 0.7 Hz, 2H), 7.14 (s, 2H), 6.70 (td, J=7.4, 1.0 Hz, 2H), 6.22 (d, J=7.8 Hz, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) ? 140.69, 137.63, 137.52, 137.39, 137.24, 136.76, 134.15, 133.78, 132.76, 132.62, 132.56, 132.00, 131.91, 131.58, 132.52, 131.14, 131.04, 130.95, 128.88, 128.75, 128.57, 128.45, 128.16, 126.40, 124.75, 119.30; .sup.31P NMR (161.5 MHz, CDCl.sub.3) ? 28.95; TLC R.sub.f 0.2 (acetone/hexanes, 1/1); HRMS calcd for C.sub.52H.sub.36O.sub.2P.sub.2: 754.2191, found: 754.2203.

(19) Data for the compound of the formula (III-2): T.sub.m 304? C. M.W.: 754.79; .sup.1H NMR (400 MHz, CDCl.sub.3) ? 7.87 (m, 4H), 7.58 (m, 6H), 7.51 (m, 6H), 7.40 (m, 8H), 7.33 (dd, J=7.6, 0.8 Hz, 2H), 7.24 (d, J=7.3 Hz, 2H), 7.03 (td, J=7.5, 1.2 Hz, 2H), 6.87 (s, 2H), 6.86 (td, J=7.6, 1.1 Hz, 2H), 6.72 (d, J=12.6 Hz, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) ? 143.94, 142.51, 138.03, 137.89, 136.70, 133.15, 133.07, 132.93, 132.25, 132.15, 131.97, 131.88, 131.84, 131.63, 130.89, 130.51, 128.60, 128.44, 128.40, 128.31, 128.19, 128.13, 127.53, 125.97, 120.19, 120.06; .sup.31P NMR (161.5 MHz, CDCl.sub.3) ? 29.04; TLC R.sub.f 0.2 (acetone/hexanes, 1/1); HRMS calcd for C.sub.52H.sub.36O.sub.2P.sub.2: 754.2191, found: 754.2197.

(20) Data for the compound of the formula (III-3): T.sub.m 304? C. M.W.; 754.79; .sup.1H NMR (400 MHz, CDCl.sub.3) ? 7.98 (d, J=11.7 Hz, 2H), 7.62 (m, 8H), 7.53 (m, 8H), 7.44 (m, 12H), 7.20 (ddd, J=12.3, 8.2, 1.4 Hz, 2H), 7.03 (s, 2H), 6.52 (dd, J=8.1, 2.1 Hz, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) ? 146.21, 141.08, 139.72, 139.59, 137.05, 133.09, 133.07, 132.85, 132.81, 132.31, 132.03, 131.93, 131.82, 131.29, 130.78, 130.64, 128.79, 128.59, 128.54, 128.47, 127.84, 126.29, 124.96, 124.83, 123.18, 123.08; .sup.31P NMR (161.5 MHz, CDCl.sub.3) ? 29.53; TLC R.sub.f0.4 (acetone/hexanes, 2/1); HRMS calcd for C.sub.52H.sub.36O.sub.2P.sub.2: 754.2191, found: 754.2177.

Example 4Preparation of Compound of Formulas (IV-1) to (IV-3)

(21) ##STR00016##

(22) A mixture of the compounds from either formula (II-1) to formula (II-3) (1.0 mmol), (3-cyanophenyl)boronic acid (0.323 g, 2.2 mmol), Pd(PPh.sub.3).sub.4 (58 mg, 0.05 mmol), and sodium carbonate (1.06 g, 10 mmol) in DME (20 mL) and distilled water (5 mL) was refluxed for 24 h under argon. The mixture was then extracted with CH.sub.2Cl.sub.2. The combined organic extracts were dried over anhydrous MgSO.sub.4 and concentrated by rotary evaporation. The crude product was purified by column chromatography on silica gel using 1:2 CH.sub.2Cl.sub.2/Hexanes as eluent to afford a white solid. Yields: 72-79%.

(23) Data for the compound of the formula (IV-1): T.sub.m 303? C. M.W.: 556.67; .sup.1H NMR (400 MHz, CDCl.sub.3) ? 57.88 (s, 2H), 7.82 (dd, J=7.8 Hz, J=0.8 Hz, 2H), 7.70-7.66 (m, 3H), 7.62 (d, J=7.6 Hz, 1H), 7.52 (t, J=7.8 Hz, 1H), 7.27 (t, J=7.4 Hz, 1H), 7.14 (s, 1H), 6.93 (t, J=7.6 Hz, 1H), 6.57 (t, J=8.0 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) ? 141.42, 140.81, 139.47, 139.20, 138.24. 137.58, 133.76, 133.49, 131.27, 130.95, 130.85, 130.40, 129.69, 129.54, 128.26, 126.57, 126.16, 125.89, 124.77, 119.49, 118.62, 113.05; TLC R.sub.f0.10 (CH.sub.2Cl.sub.2/hexanes, 1/4); HRMS calcd for C.sub.42H.sub.24N.sub.2: 556.1939, found: 556.1945.

(24) Data for the compound of the formula (IV-2): T.sub.m 297? C. M.W.: 556.67; .sup.1H NMR (400 MHz, CDCl.sub.3) ? 6.72 (d, J=1.2 Hz, 2H), 7.06 (s, 2H), 7.43-7.51 (m, 4H), 7.55-7.63 (m, 12H), 7.75-7.69 (m, 4H); .sup.13C NMR (100 MHz, CDCl.sub.3) ? 142.93, 142.09, 140.15, 139.35, 137.52, 136.73, 133.97, 132.08, 131.07, 130.88, 130.52, 130.48, 129.64, 129.23, 128.89, 128.06, 127.16, 126.45, 124.15, 120.34, 118.97, 113.04; TLC R.sub.f 0.40 (CH2Cl2/hexanes, 1/2): HRMS calcd for C.sub.42H.sub.24N.sub.2: 556.1939, found: 556.1938.

(25) Data for the compound of the formula (IV-3): T.sub.m 302? C. M.W.: 556.67; .sup.1H NMR (400 MHz, CDCl.sub.3) ? 6.58 (d, J=8.4 Hz, 2H), 7.08 (s, 2H), 7.17 (dd, J=8.4 Hz, 1.6 Hz, 2H), 7.46-7.64 (m, 12H), 7.51 (dd, J=7.6 Hz, 1.2 Hz, 2H), 7.91 (dd, J=4.8 Hz, 1.2 Hz, 4H). .sup.13C NMR (100 MHz, CDCl.sub.3) ? 143.24, 142.29, 141.10, 138.54, 137.80, 133.70, 131.78, 131.49, 131.00, 130.77, 129.82, 128.91, 128.79, 127.92, 127.03, 125.97, 125.92, 118.99, 117.93, 113.20: TLC R.sub.f0.38 (CH.sub.2Cl.sub.2/hexanes, 1/2); HRMS calcd for C.sub.42H.sub.24N.sub.2: 556.1939, found: 556.1943.

(26) Steady-State Photophysical Measurements

(27) Absorption spectra were measured on a SP-8001 Diode Array spectrometer by using spectrophotometric grade CH.sub.2Cl.sub.2 (10 mM in CH.sub.2Cl.sub.2). Emission spectra (in 10 mM) were measured on a FP-6500 luminescence spectrometer upon excitation at the absorption maxima, of the longest absorption band in the same solvent. The emission spectra measured in CH.sub.2Cl.sub.2 (10 mM) were normalized by their emission maxima to the same intensity (maximum intensity 1). Fluorescence quantum yield (?.sub.f, %) calculation were integrated emission area of the fluorescent spectra and compared the value to the same area measured for Coumarin 1.sup.2c (?.sub.f=0.90, CH.sub.2Cl.sub.2) or Coumarin 6 (?.sub.f=0.78, EtOH) in CH.sub.2Cl.sub.2 (in 10 mM). The quantum yields are calculated by using the following equation 1. Where A stands for area of fluorescent emission for sample (i.e. the compounds of formulas (III-1) to (III-3)) and Coumarin 1 or Coumarin 6; a is absorbance for sample and Coumarin 1 or Coumarin 6; and n is the refractive indices of solvent for sample and Coumarin 1 or Coumarin 6 (the refractive index (n) for CH.sub.2Cl.sub.2=1.42; for EtOH=1.36).
?.sup.sample.sub.f=(A.sub.sample/A.sub.standard)?(a.sub.standard/a.sub.sample)?(n.sub.sample/n.sub.sample)?(n.sub.sample/n.sub.standard).sup.2??.sup.standard.sub.f[Equation 1]
Cyclic Voltammetry (CV) Measurements

(28) CV experiments were carried out with 1.0 mM of one substrate in a given anhydrous, degassed solvent containing 0.1 M tetrabutylammonium perchlorate or phosphate (n-Bu.sub.4NClO.sub.4 or n-Bu.sub.4NPF.sub.6) as a supporting electrolyte on a Chinstruments CH1604A potentiostat. A platinum wire electrode was used as a counter electrode, and a glassy carbon electrode was used as a working electrode. Ag/AgCl was used as a reference electrode.

(29) Differential Scanning Calorimetry (DSC) Analyses

(30) DSC measurements were performed on a SEIKO SSC 5200 DSC Computer/Thermal Analyzer. The samples were first heated (20? C./min) to melt and then quenched with liquid nitrogen. Glass transition temperatures (T.sub.g) were recorded by heating (10? C./min) the cooled samples.

(31) Thermogravimetric Analyses (TGA)

(32) TGA measurements were performed on a SEIKO TG/DTA200 instrument by the Northern Instrument Center of Taiwan. Melting points were measured on a Hargo MP-2D instrument.

(33) Property Evaluations of Compounds of Formulas (III-1) to (III-3) and (IV-1) to (IV-3)

(34) The data of glass transition temperature (T.sub.g), decomposition temperature (T.sub.d), the longest peak wavelength value of absorption spectrum (?.sub.max), and the longest peak wavelength value of photoluminescence spectrum (PL ?.sub.max) of the compounds of formulas (III-1) to (III-3) and (IV-1) to (IV-3) are measured and recorded in the following Table 1. From the Table (1), it is able to know that these compounds provided by the present invention have glass transition temperatures (T.sub.g) ranged from 127? C. to 162? C. and decomposition temperatures (T.sub.d) ranged from 350? C. to 436? C. That means the compounds of provided by the present invention possess excellent thermal stability, and are not easy to decompose under high voltage and high current density operation conditions.

(35) TABLE-US-00001 TABLE 1 T.sub.g T.sub.d ?.sub.max PL?.sub.max Compound (? C.) (? C.) (nm) (nm) Formula (III-1) 140 350 308 491 Formula (III-2) 143 375 303 459 Formula (III-3) 162 357 329 473 Formula (IV-1) 143 436 320 469, 503 Formula (IV-2) 127 363 334 468, 496 Formula (IV-3) 161 346 338 464, 497

(36) Moreover, the oxidation potential and the reduction potential of the compounds provided by the present invention can be measured by way of cyclic voltammetry (CV); therefore, the highest occupied molecular orbital energy level (E.sub.HOMO) and lowest unoccupied molecular orbital energy level (E.sub.LUMO) of the compounds provided by the present invention can also be calculated based on the measured oxidation potential (E.sub.1/2.sup.ox) and the reduction potential (E.sub.1/2.sup.red). With reference to following Table 2, E.sub.1/2.sup.ox, E.sub.1/2.sup.red, E.sub.HOMO, and E.sub.LUMO of the compounds of the present invention are recorded. From the Table 2, the persons skilled in OLED material art are able to know that the compounds provided by the present invention have the E.sub.HOMO ranged from 5.95 eV to 6.19 eV and the E.sub.LUMO ranged from 2.67 eV to 2.96 eV. Moreover, the compounds provided by the present invention also have the oxidation potentials ranged from 1.01 V to 1.16 V and the reduction potentials ranged from ?1.91 V to ?2.29 V.

(37) TABLE-US-00002 TABLE 2 E.sub.?.sup.ox E.sub.?.sup.red E.sub.g E.sub.HOMO E.sub.LUMO Compound (V) (V) (eV) (eV) (eV) Formula (III-1) 1.09 ?2.29 3.40 6.19 2.79 Formula (III-2) 1.05 ?2.02 3.28 6.15 2.87 Formula (III-3) 1.16 ?1.91 3.20 6.16 2.96 Formula (IV-1) 1.04 ?2.17 3.35 6.14 275 Formula (IV-2) 1.01 ?2.18 3.37 5.98 2.67 Formula (IV-3) 1.07 ?2.12 3.25 5.95 2.82

(38) Furthermore, on order to prove that the compounds of the present invention can indeed be applied in OLEDs for being as a hole-blocking type electron transport layer, a plurality of OLED devices for control groups and experiment groups have been designed and manufactured.

(39) All the materials were either commercially available or synthesized as described in this experiment and were subjected to gradient sublimation under high vacuum prior to use. The substrate was an indium tin oxide (ITO) coated glass sheet with a sheet resistance of ?30 W/. Pre-patterned ITO substrates were cleaned sequentially by sonication in a detergent solution, doubly distilled water, and EtOH for 5 min in turn before being blown dry with a stream of nitrogen. The ITO substrate was then treated with oxygen plasma for 5 min before being loaded into the vacuum chamber. The organic layers were deposited thermally at a rate of 0.1-0.3 nm/s in a chamber (ULVAC, TU-12RE) under a pressure of 5?10.sup.?6 Torr. Device were constructed with 40 nm of the hole transporting layer (HTL), 40 nm of the light-emitting layer (LEL), 10 nm of the hole-blocking layer (HBL), 40 nm of the electron-transporting layer (ETL), 1 nm of LiF as the electron-injecting layer (EIL), and 150 nm of Al as the cathode, respectively. In addition, 1,4,5,8,9,11-Hexaazatriphenylene-hexacarbonitrile (HATCN) is used as the HIL; 4,4-Cyclohexylidenebis [N,N-bis(4-methylphenyl)benzenamine] (TAPC) is used as the HT01. Herein, the material used in each layer is summarized in the following Table 3.

(40) TABLE-US-00003 TABLE 3 Cathode EIL ETL HBL LEL HTL Anode Embodiment 1 Al LiF Formula Formula Green TAPC HIL/ITO (III-1) (III-1) phosphorescent Embodiment 2 Al LiF Formula Formula Green TAPC HIL/ITO (III-2) (III-2) phosphorescent Embodiment 3 Al LiF Formula Formula Green TAPC HIL/ITO (III-3) (III-3) phosphorescent Embodiment 4 Al LiF Formula Formula Green TAPC HIL/ITO (IV-1) (IV-1) phosphorescent Embodiment 5 Al LiF Formula Formula Green TAPC HIL/ITO (IV-2) (IV-2) phosphorescent Embodiment 6 Al LiF Formula Formula Green TAPC HIL/ITO (IV-3) (IV-3) phosphorescent Comparative Al LiF BmPyPb BmPyPb Green TAPC HIL/ITO embodiment 1A phosphorescent Comparative Al LiF DPyPA DPyPA Green TAPC HIL/ITO embodiment 1B phosphorescent Comparative Al LiF TPBi TPBi Green TAPC HIL/ITO embodiment 1C phosphorescent Comparative Al LiF ET01 ET01 Green TAPC HIL/ITO embodiment 1D phosphorescent Embodiment 7 Al LiF Formula Formula Green NPB/HT01 HIL/ITO (III-3) (III-3) phosphorescent Embodiment 8 Al LiF Formula Formula Green NPB/HT01 HIL/ITO (IV-3) (IV-3) phosphorescent Comparative Al LiF BmPyPb BmPyPp Green NPB/HT01 HIL/ITO embodiment 2 phosphorescent Comparative Al LiF ET01 ET01 Green NPB/HT01 HIL/ITO embodiment 3 phosphorescent

(41) In the Table 3, BmPyPb is the abbreviation of 1,3-bis(3,5-dipyrid-3-yl-phenyl)benzene, DPyPA is the abbreviation of 9,10-bis(3-(pyridin-3-yl)phenyl)anthracene, mid TPBi is the abbreviation of 1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl)benzene. In addition, ET01 is represented by the following formula (TV) and the green phosphorescent dopant is Ir(ppy).sub.3 along with 11-(4,6-diphenyl-1,3,5-triazin-2-yl)-12-phenyl-11,12-dihydroindolo[2,3-a]carbazole as the host which is represented by the following formula (V).

(42) ##STR00017##

(43) Furthermore, it is able to know that the materials of TPBi, DPyPA, BmPyPb, and ET01 recorded in the Table 3 are also used as OLED device's electron transport layers. However, the present invention is not limited thereto.

(44) FIG. 2 is a perspective view showing the OLED devices provided above. The OLED device of the present invention comprises: a first electrode 12; a second electrode 18; and an organic layer disposed between the first electrode 12 and the second electrode 18. Herein, the first electrode 12 is a cathode, and a substrate 11 is disposed therebelow. The second electrode 18 is an anode. The organic layer comprises: an election-injection layer 13, an electrode-transporting layer 14, a hole-blocking layer 15, a light-emitting layer 16, and a hole transporting layer 17, sequentially laminated on the first electrode 12.

(45) Herein, Current-voltage-light intensity (I-V-L) characteristics and EL spectra were measured and recorded by PRECISE GAUGE, EL-1003; and the turn-on voltage (V.sub.on), the external quantum efficiency (?.sub.ext), the current efficiency (?.sub.c), the power efficiency (?.sub.p), and the maximum luminance (L.sub.max) of the OLED devices are listed in the following Table 4.

(46) TABLE-US-00004 TABLE 4 ?.sub.max Von ?.sub.ext ?.sub.p/?.sub.c L.sub.max (nm) (V) (%) (%) (cd/m.sub.2) Embodiment 1 516 2.1 10.8 38.8/20.9 109,500 Embodiment 2 512 2.2 13.3 46.7/20.7 123,800 LT.sub.50, 2,700 h Embodiment 3 516 2.2 13.2 46.9/18.0 62,840 Embodiment 4 512 2.1 10.5 50.6/37.2 127,610 LT.sub.50, 14,700 h Embodiment 5 512 2.2 11.8 49.4/36.7 126,353 Embodiment 6 512 2.4 10.9 48.9/36.1 125,789 Comparative 516 2.5 6.3 22.8/18.0 142,100 LT.sub.50, embodiment 1A 1,000 h Comparative 516 3.0 10.2 37.8/24.0 40,700 embodiment 1B Comparative 516 3.0 6.9 24.7/22.0 37,640 embodiment 1C Comparative 512 2.0 14.5 51.1/31.2 124,200 LT.sub.50, embodiment 1D 13,500 h Embodiment 7 516 5.0 11.9 40.7/25.6 41,000 LT.sub.50, 3,022 h Embodiment 8 516 5.0 12.5 43.5/28.6 52,700 LT.sub.50, 6,040 h Comparative 516 4.5 10.8 36.8/25.7 42,150 embodiment 2 Comparative 516 5.5 7.04 26.2/14.9 26,000 LT.sub.50, embodiment 3 600 h

(47) With reference to the measured data of the green phosphorescent OLED devices in the Table 4, one can find that the OLED devices using single hole transport layer of Embodiments 1-3 and Embodiments 4-6 show excellent ?.sub.ext, ?.sub.c, ?.sub.p, and L.sub.max and are much superior to the OLED devices using single hole transport layer of Comparative embodiment 1A, Comparative embodiment 1B, and Comparative embodiment 1C. Among them, Embodiment 2 (Compound of formula (III-2)) and Embodiment 5 (Compound of formula (IV-2)) show the best and comparable results with that for Comparative embodiment 1D. For the OLED device of Embodiment 2, the ?.sub.ext is 13.3%, ?.sub.0 is 46.7 cd/A, ?.sub.c is 20.7 lm/w, and L.sub.max is 123,800 cd/m.sup.2. For the OLED device of Embodiment 4, the ?.sub.ext is 10.5%, ?.sub.p is 50.6 cd/A, ?.sub.c is 37.2 lm/w, and L.sub.max is 127,600 cd/m.sup.2.

(48) In addition, the data shown in Table 1 also reveal that the OLED devices using single hole transport layer of Embodiments 7 and 8 show excellent ?.sub.ext, ?.sub.c, ?.sub.p, and L.sub.max and are superior to the OLED devices using complex (i.e., double) hole transport layer of Comparative embodiment 2 and Comparative embodiment 3. Moreover, the OLED device using complex (double) hole transport layer of Embodiment 7 (Compound of formula (III-3)) and Embodiment 8 (Compound of formula (IV-3)) also shows excellent ?.sub.ext, ?.sub.c, ?.sub.p, and L.sub.max, which is superior to the OLED devices using complex (i.e., double) hole transport layer of Comparative embodiment 2 and Comparative embodiment 3.

(49) Furthermore, device life time evaluation test for the green phosphorescent OLEDs have also been completed based on a starting luminance of 10,000 cd/cm.sup.2. Life time evaluation test results reveal that the decay half lifetimes (LT.sub.50) of the green phosphorescent OLED for Embodiment 4, Embodiment 7 and Embodiment 8 are 14,700 hours, 3,022 hours and 6,040 hours, respectively. In addition, the decay half lifetime (LT.sub.50) for the green phosphorescent OLEDs of Comparative embodiment 1A, Comparative embodiment 1D, and Comparative embodiment 3 are respectively measured as 1,000, 13,500, and 600 hours.

(50) In conclusion, the compounds of the present invention have glass transition temperatures ranged from 127? C. to 162? C., decomposition temperatures ranged from 350? C. to 436? C., reversible electron transport, property, and balanced charges motilities.

(51) Moreover, a variety of experimental data have proved that the compounds of the present invention can indeed be used as a hole-blocking type electron-transporter for OLEDs; moreover, the experimental data also reveal that the OLEDs using the compounds of the present invention can show excellent external quantum efficiency (?.sub.ext), current efficiency (?.sub.c), power efficiency (?.sub.p), maximum luminance (L.sub.max), and device lifetime performances better than the conventional or commercial OLEDs.

(52) Except for the aforementioned OLED devices, the present invention also provides an organic solar cell, which is shown in FIG. 3. The organic solar cell of one embodiment of the present invention comprises: a first electrode 21; a second electrode 22; and an organic layer 23 disposed between the first electrode 21 and the second electrode 22 and comprising any one of the compounds of the formulas (III-1) to (III-3) or the formulas (IV-1) to (IV-3). In the organic solar cell of the present invention, the organic layer 23 is served as a carrier transport layer.

(53) Except for the aforementioned OLED device and organic solar cell device, the compounds provided by the present invention can be applied to various organic electronic devices, such as an organic thin film transistor, an organic photodetector, a flat panel display a computer monitor, a television, a billboard, a light for inferior or exterior illumination, a light for interior or exterior signaling, a heads up display a fully transparent display, a flexible display, a laser printer, a telephone, a cell phone, a tablet computer, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display a vehicle, a large area wall, a theater or stadium screen, or a sign. However, the present invention is not limited thereto.

(54) Although the present invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed.