Synthesis and Electroluminescence Property of Pyrene Derivatives Including Dibenzothiophene and Imidazole Moiety.

Pyrene, imidazole and dibenzothiophene were used to synthesize new blue emitters of 1-(4-Dibenzothiophen-2-yl-phenyl)-4,5-diphenyl-2-pyren-1-yl-1H-imidazole (DDPI) and 1-(3-Dibenzothiophen-4-yl-phenyl)-2-pyren-1-yl-1H-phenanthro[9,10-d]imidazole (DPPI). The optical properties of synthesized compounds were measured by UV-visible absorption and PL spectra. In the vacuum deposited film state, the PL maximum value is 463 nm for DDPI and 455, 471 nm for DPPI. The device using DDPI as emitting material showed CE of 2.38 cd/A, PE of 1.38 lm/W, and EQE of 1.54%, device using DPPI as emitting material exhibited CE of 3.65 cd/A, PE of 2.31 lm/W, and EQE of 3.07%. Also, OLED devices of DDPI and DPPI devices exhibited CIE coordinate of (0.20, 0.23) and (0.16, 0.16).

New Pyrene Derivatives Having Rigid Imidazole Moiety for Blue Emitters.

Pyrene, imidazole and dibenzofuran were used to synthesize new blue emitters of 1-(4-(dibenzo[b,d]furan-4-yl)phenyl)-2-(pyren-1-yl)-1H-phenanthro[9,10-d]imidazole (BFP-PI) and 1-(4-(dibenzo[b,d]furan-4-yl)phenyl)-4,5-diphenyl-2-(pyren-1-yl)-1H-imidazole (BFP-DPI). In the film state, BFP-PI and BFP-DPI show photoluminescence (PL) maximum values of 462 nm and 459 nm. The relative PL quantum efficiency (PLQY) of BFP-PI and BFP-DPI is 89.16% and 79.2% by using reference compound of 9,10-diphenylanthracene. The device using BFP-PI in the non-doped state as emitting material showed current efficiency (C.E.) of 3 cd/A and external quantum efficiency (E.Q.E.) of 2.15%, and the device using BFP-DPI as emitting material exhibited C.E. of 2.64 cd/A and E.Q.E. of 1.6%.

Synthesis and Electroluminescence Properties of New Type Multi-Chromophore Emitting Materials for Organic Light-Emitting Diodes.

New three emitting compounds, AK-1, AK-2 and AK-3 including diazocine moiety were synthesized through Suzuki-coupling reaction. Physical properties such as optical, electroluminescent properties were investigated. UV-visible spectrum of AK-1, AK-2 and AK-3 in film state showed maximum 392, 393 and 401 nm. PL spectrum of AK-1, AK-2 and AK-3 showed maximum emission wavelength of 472, 473 and 435 nm. Three compounds were used as EML in OLED device: ITO/2-TNATA (60 nm)/NPB (15 nm)/EML (35 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm). AK-3 OLED device showed C.I.E value of (0.18, 0.26) and luminance efficiency of 0.51 cd/A at 10 mA/cm2. New derivatives including diazocine moiety were introduced as OLED emitting material and the EL efficiency was increased by the proper combination of core and side group.

Synthesis and Electroluminescent Properties of New Dibenzo-Diazocine Derivatives.

AK-1NA and AK-2NA based on dibenzo-diazocine and anthracene moieties were designed and synthesized. Normalized UV-visible spectra of AK-1NA and AK-2NA in film state showed maximum absorption wavelength of 394 and 393 nm. PL spectra of AK-1NA and AK-2NA showed maximum emission wavelength of 429 and 444 nm. At a current density of 10 mA/cm2, OLED devices of AK-1NA and AK-2NA exhibited luminance efficiency of 2.39 and 1.50 cd/A, power efficiency of 1.01 and 0.81 lm/W. Also, OLED devices of AK-1NA and AK-2NA devices exhibited CIE(x, y ) of (0.16, 0.22) and (0.23, 0.42).

New ambipolar blue emitting materials based on amino coumarin derivatives with high efficiency for organic lightemitting diodes.

New blue emitting materials, 7-diphenylamino-4-methyl-coumarin (DPA-MC) and amino-tri(4-methylcoumarin) (T-MC) including coumarin moiety were synthesized by Ullman reaction. Optical and electronic properties were examined by UV-Vis. Absorption spectrum, PL spectrum, and cyclic voltammetry. UV-Vis. spectra of DPA-MC and T-MC in a film state showed maximum absorption wavelengths of 382 nm and 399 nm, respectively. PL spectra of DPA-MC and T-MC show maximum emission wavelengths of 463 nm and 481 nm respectively. Non-doped OLED devices were fabricated by using the synthesized materials as an emitting material layer. DPA-MC compound showed highly efficient luminescence properties. EL spectrum of DPA-MC exhibited a maximum value of 463 nm and DPA-MC device provided luminescence efficiency of 3.83 cd/A, power efficiency of 2.46 Im/W, external quantum efficiency of 3.71% and CIE coordinates of (0.154, 0.190) at a current density of 10 mA/cm2. In particular, Power efficiency increased by more than 1.6 times in DPA-MC (2.46 ImNW), which is higher than commercialized material, DPVBi (1.46 Im/W). High EL performance might come from ambipolar effects of a molecular structure.

Elongation of lifetime of the charge-separated state of ferrocene-naphthalenediimide-[60]fullerene triad via stepwise electron transfer.

Photoinduced electron-transfer processes of a newly synthesized rodlike covalently linked ferrocene-naphthalenediimide-[60]fullerene (Fc-NDI-C(60)) triad in which Fc is an electron donor and NDI and C(60) are electron acceptors with similar first one-electron reduction potentials have been studied in benzonitrile. In the examined Fc-NDI-C(60) triad, NDI with high molar absorptivity is considered to be the chromophore unit for photoexcitation. Although the free-energy calculations verify that photoinduced charge-separation processes via singlet- and triplet-excited states of NDI are feasible, transient absorption spectra observed upon femtosecond laser excitation of NDI at 390 nm revealed fast and efficient electron transfer from Fc to the singlet-excited state of NDI ((1)NDI*) to produce Fc(+)-NDI(•-)-C(60). Interestingly, this initial charge-separated state is followed by a stepwise electron transfer yielding Fc(+)-NDI-C(60)(•-). As a result of this sequential electron-transfer process, the lifetime of the charge-separated state (τ(CS)) is elongated to 935 ps, while Fc(+)-NDI(•-) has a lifetime of only 11 ps.

Supramolecular tetrad of subphthalocyanine-triphenylamine-zinc porphyrin coordinated to fullerene as an "antenna-reaction-center" mimic: formation of a long-lived charge-separated state in nonpolar solvent.

We report here the formation of a long-lived charge-separated state of a self-assembled donor-acceptor tetrad, formed by axial coordination of a fulleropyrrolidine appended with an imidazole coordinating ligand (C(60)Im) to the zinc center of a subphthalocyanine-triphenylamine-zinc porphyrin (SubPc-TPA-ZnP), as a charge-stabilizing antenna reaction center mimic in toluene. The subphthalocyanine and triphenylamine entities, with their high-energy singlet states, act as an energy-transferring antenna unit to produce a singlet zinc porphyrin. The formation constant for the self-assembled tetrad was determined to be 1.0 x 10(4) M(-1), suggesting a moderately stable complex formation. The geometric and electronic structures of the covalently linked SubPc-TPA-ZnP triad and self-assembled SubPc-TPA-ZnP:C(60)Im tetrad were examined by using an ab initio B3LYP/6-31G method. The majority of the highest occupied frontier molecular orbital was found over the ZnP and TPA entities, whereas the lowest unoccupied molecular orbital was located over the fullerene entity, suggesting the formation of the radical-ion pair (SubPc-TPA-ZnP(*+):C(60)Im(*-)). The redox measurements revealed that the energy level of the radical-ion pair in toluene is located lower than that of the singlet and triplet states of the zinc porphyrin and fullerene entities. The femtosecond transient absorption measurements revealed fast charge separation from the singlet porphyrin to the coordinated C(60)Im with a lifetime of 1.1 ns. Interestingly, slow charge recombination (1.6 x 10(5) s(-1)) and the long lifetime of the charge-separated state (6.6 micros) were obtained in toluene by utilizing the nanosecond transient measurements.

Stabilization of the charge-separated States of covalently linked zinc porphyrin-triphenylamine-[60]fullerene.

Spectroscopic, redox, computational, and electron transfer reactions of the covalently linked zinc porphyrin-triphenylamine-fulleropyrrolidine system are investigated in solvents of varying polarity. An appreciable interaction between triphenylamine and the porphyrin pi system is revealed by steady-state absorption and emission, redox, and computational studies. Free-energy calculations suggest that the light-induced processes via the singlet-excited porphyrin are exothermic in benzonitrile, dichlorobenzene, toluene, and benzene. The occurrence of fast and efficient charge-separation processes ( approximately 10(12) s(-1)) via the singlet-excited porphyrin is confirmed by femtosecond transient absorption measurements in solvents with dielectric constants ranging from 25.2 (benzonitrile) to 2.2 (benzene). The rates of the charge separation processes are much less solvent-dependent, which suggests that the charge-separation processes occur at the top region of the Marcus parabola. The lifetimes of the singlet radical-ion pair (70-3000 ps at room temperature) decrease substantially in more polar solvents, which suggests that the charge-recombination process is occurring in the Marcus inverted region. Interestingly, by utilizing the nanosecond transient absorption spectral technique we can obtain clear evidence about the existence of triplet radical-ion pairs with relatively long lifetimes of 0.71 mus (in benzonitrile) and 2.2 mus (in o-dichlorobenzene), but not in toluene and benzene due to energetic considerations. From the point of view of mechanistic information, the synthesized zinc porphyrin-triphenylamine-fulleropyrrolidine system has the advantage that both the lifetimes of the singlet and triplet radical-ion pair can be determined.

Synthesis and photoinduced intramolecular processes of light-harvesting silicon phthalocyanine-naphthalenediimide-fullerene connected systems.

Photoinduced intramolecular processes of a newly synthesized pentad composed of silicon phthalocyanine (SiPc) that is connected with two units of naphthalenediimide (NDI) and fullerene C(60) to form SiPc-(NDI)(2)-(C(60))(2) have been studied and the results are compared with the reference compounds, namely, the SiPc-(NDI)(2) triad and NDI-C(60) dyad. Upon photoexcitation, the main quenching pathway in polar solvents involved electron transfer via the singlet excited states of SiPc-(NDI)(2)-(C(60))(2) and SiPc-(NDI)(2), but not NDI-C(60) for which the energy transfer is dominant. The occurrence of electron-transfer processes of SiPc-(NDI)(2)-(C(60))(2) and SiPc-(NDI)(2) were studied by time-resolved emission and transient absorption techniques and confirmed by redox measurements and molecular orbital calculations with ab initio B3 LYP/3-21G(*) methods. Fast and efficient charge-separation processes via the singlet excited states of NDI and SiPc were monitored, followed by charge recombination to populate the C(60) and SiPc triplet states. The lifetimes of charge-separated states were estimated as 1000 and 250 ps for SiPc-(NDI)(2)-(C(60))(2) and SiPc-(NDI)(2), respectively.

Isolation and characterization of a novel adenosine deaminase inhibitor, IADA-7, from Bacillus sp. J-89.

Adenosine deaminase (ADA), an enzyme involved in purine metabolism, catalyzes the hydrolytic breakdown of adenosine into inosine and free ammonia. ADA regulation has been targeted as a potential therapeutic agent for viral infections and lymphoproliferative disorders. In this study, we isolated a novel ADA inhibitor from a culture of Bacillus sp. J-89, and evaluated its anti-proliferative activity on human cancer cell lines. The ADA inhibitor was deduced as a 2-N-methyl-2,4-diazacycloheptanone by analyses of UV, IR, EI-MASS, (1)H-NMR, (13)C-(1)H NMR, and (13)C-NMR spectroscopy, and was designated IADA-7. IADA-7 was shown to inhibit purified mammalian and Actinomyces ADA. IADA-7 also inhibited the proliferation of both Jurkat T cells (IC(50) = 15 microg/mL) and J 82 (human transitional-cell carcinoma, bladder) cells (IC(50) = 25 microg/mL). In Jurkat T cells, apoptosis with 15 microg/mL IADA-7 for 24 and 48 hours was 9 and 13%, respectively. These results suggest that IADA-7 can inhibit ADA activity in multiple species and that it may represent a good candidate as an anti-cancer therapeutic agent due to its demonstrated anti-proliferative activity on cancer cells.

Effect of dual fullerenes on lifetimes of charge-separated States of subphthalocyanine-triphenylamine-fullerene molecular systems.

Photoinduced intramolecular electron-transfer events of the newly synthesized subphthalocyanine-triphenylamine-fullerene triad (SubPc-TPA-C60) and subphthalocyanine-triphenylamine-bisfullerene tetrad (SubPc-TPA-(C(60))(2)) were studied. The geometric and electronic structures of the triad were probed by ab initio B3LYP/3-21G method, which predicts SubPc-TPA(*+)-C(60)(*-) as a stable charge-separated state. The photoinduced events via the excited singlet state of SubPc were monitored by time-resolved emission measurements as well as transient absorption techniques. Efficient charge-separations via the excited states of SubPc were observed with the rates of approximately 10(10) s(-)1. Compared with the SubPc-TPA dyad, a long-lived charge-separated state was observed for the SubPc-TPA-C(60) triad with the lifetime of the radical ion pairs (tau(RIP)) of 670 ns in benzonitrile. Interestingly, further charge stabilization was achieved in the charge-separated state of SubPc-TPA-(C(60))(2), in which the tau(RIP) was found to be 1050 ns in benzonitrile.

Synthesis and Electroluminescence Property of New Hexaphenyl Benzene Derivatives Including Emitting Core for OLED.

Three new emitting compounds of 5P-2TPA, 5P-2An and 5P-2Py for OLED based on hexaphenyl benzene moiety were synthesized. Physical properties were systematically examined by the change of the substitution groups of the synthesized materials. Photoluminescence (PL) spectrum of the synthesized materials showed maximum emitting wavelengths of about 437~488 nm in solution state and 457~516 nm in film state, indicating blue emission color. OLED devices were fabricated by the synthesized compounds using vacuum deposition process as an emitting layer. Device structure was ITO/2-TNATA 60 nm/NPB 15 nm/EML 35 nm/TPBi 20 nm/LiF 1 nm/Al 200 nm. External quantum efficiencies and CIE values of 5P-2TPA, 5P-2An and 5P-2Py were 3.34, 1.06 and 2.06% and (0.14, 0.12), (0.23, 0.45) and (0.24, 0.45), respectively. The three compounds exhibited thermal stablility with high Td of 426 °C, 449 °C and 467 °C.

Long-Range π-Conjugation in Phenothiazine-containing Donor-Acceptor Dyes for Application in Dye-Sensitized Solar Cells.

Four organic donor-π-bridge-acceptor dyes containing phenothiazine as a spacer and cyanoacrylic acid as an acceptor were synthesized and tested as sensitizers in dye-sensitized solar cells (DSCs). The influence of iodide- and cobalt-based redox electrolytes on the photovoltaic device performance was investigated. In these new dyes, systematic π-conjugation was extended by inserting one or two phenothiazine moieties and investigated within the context of the resulting photoinduced charge-transfer properties. A detailed investigation, including transient absorption spectroscopy and quantum chemical methods, provided important information on the role of extended π-conjugation on the photophysical properties and photovoltaic device performance. Overall, the results showed that the extension of π-conjugation by one phenothiazine unit resulted in the best device performance owing to reduced recombination rates, whereas extension by two phenothiazine units reduced dye adsorption on TiO2 probably owing to the increase in molecular size. The performance of the dyes in DSCs was found to be a complex interaction between dye structure and size.

New hole transporting materials based on hexaarylbenzene and aromatic amine moiety for organic light-emitting diodes.

Three different new hole transport compounds, namely DPAP-TB, 1-PNAP-TB and 2-PNAP-TB, were synthesized by Sonogashira coupling and Diels-Alder reaction. Synthesized materials exhibited high Tg in the range of 118 to 133 °C. These values are higher than that of NPB, which is commonly used as a hole transporting material. OLED devices were fabricated by the synthesized compounds using the solution process as a hole transporting layer. Device structure was ITO/PEDOT:PSS (40 nm)/synthesized compounds or NPB (20 nm)/Alq3 (70 nm)/LiF/Al. Luminance efficiencies and external quantum efficiencies of DPAP-TB, 1-PNAP-TB and 2-PNAP-TB devices were 3.98, 4.62, 4.22 cd/A, and 1.35, 1.56, 1.43% at 20 mA/cm2, respectively. In luminance efficiency and external quantum efficiency, 1-PNAP-TB especially had superior property to NPB.

Synthesis and electroluminescence property of new hexaphenylbenzene derivatives including amine group for blue emitters.

Three new blue-emitting compounds of 5P-VA, 5P-VTPA, and 5P-DVTPA for organic light-emitting diode (OLED) based on hexaphenylbenzene moiety were demonstrated. Physical properties by the change of the substitution groups of the synthesized materials were systematically examined. Photoluminescence spectrum of the synthesized materials showed maximum emitting wavelengths of about 400 to 447 nm in solution state and 451 to 461 nm in film state, indicating deep blue emission color. OLED devices were fabricated by the synthesized compounds using vacuum deposit process as an emitting layer. The device structure was ITO/2-TNATA 60 nm/ NPB 15 nm/ EML 35 nm/ TPBi 20 nm/ LiF 1 nm/ Al 200 nm. External quantum efficiencies and CIE values of 5P-VA, 5P-VTPA, and 5P-DVTPA were 1.89%, 3.59%, 3.34%, and (0.154, 0.196), (0.150, 0.076), (0.148, 0.120), respectively. 5P-VTPA and 5P-DVTPA exhibited superior highly blue quality and thermal property such as high Td of 448°C and 449°C.

Silicon-phthalocyanine-cored fullerene dendrimers: synthesis and prolonged charge-separated states with dendrimer generations.

Silicon-phthalocyanine-cored fullerodendrimers with up to eight fullerene substituents (SiPc-n C(60); n=2, 4, and 8) have been synthesized. Photophysical properties of newly synthesized SiPc-n C(60) have been investigated by time-resolved fluorescence and transient absorption analysis with pulsed laser light. Laser photolysis measurements suggest the occurrence of a charge-separation process from (1)SiPc* to the C(60) subunits. The nanosecond transient absorption spectra in the near-IR region indicate that the lifetimes of the formed radical ion pairs are prolonged on the order of SiPc-8 C(60)>SiPc-4 C(60)>SiPc-2 C(60), which may be related to the electron migration among the C(60) subunits. The usefulness of SiPc-n C(60) as light-harvesting systems, evaluated as a ratio of the rates of charge recombination to those of charge separation, increases markedly with the dendrimer generation.