• Bulletin of the Korean Chemical Society
• /
• v.31 no.8
• /
• pp.2309-2314
• /
• 2010

Design and syntheses of four red phosphorescent heteroleptic cationic iridium(III) complexes containing two substituted phenylquinoxaline (pqx) or benzo[b]thiophen-2-yl-pyridin (btp) main ligands and one 2,2'-biimidazole (H2biim) ancillary ligand are reported: [$(pqx)_2$Ir(biim)]Cl (1), [$(dmpqx)_2$Ir(biim)]Cl (2), [$(dfpqx)_2$Ir(biim)]Cl (3), [$(btp)_2$Ir(biim)]Cl (4). Complex 1 showed a distorted octahedral geometry around the iridium(III) metal ion with cis metallated carbons and trans nitrogen atoms. The absorption, emission and electrochemical properties were systematically evaluated. The complexes exhibited red phosphorescence in the spectral range of 580 to 620 nm with high quantum efficiencies of 0.58 - 0.78 in both solution and solid-state at room temperature depending on the cyclometalated main ligands. The cyclic voltammetry of the complexes (1-3) showed a metal-centered irreversible oxidation in the range of 1.40 to 1.90 V as well as two quasi reversible reduction waves from -1.15 to -1.45 V attributed to the sequential addition of two electrons to the more electron accepting heterocyclic portion of two distinctive cyclometalated main ligands, whereas complex 4 showed a reversible oxidation potential at 1.24 V and irreversible reduction waves at -1.80 V.

• Journal of Information Display
• /
• v.3 no.1
• /
• pp.6-10
• /
• 2002

We have synthesized a new green Ir(III) complex fac-tris-(3-methyl-2-phenyl pyridine)iridium(III) $Ir(mpp)_3$ and fabricated phosphorescent polymer light-emitting device using it as a triplet emissive dopant in PVK. $Ir(mpp)_3$ showed absorption centered at 388 nm corresponding to the $^1MLCT$ transition as .evidenced by its extinction coefficient of the order of $10^3{\cdot}$ From the PL and EL spectra of the $Ir(mpp)_3$ doped PVK film, the emission maximum was observed at 523 nm, due to the radiative decay from the $^3MLCT$ state to the ground state, confirming a complete energy transfer from PVK to $Ir(mpp)_3$. The methyl substitution has probably caused a red shift in the absorption and emission spectrum compared to $Ir(mpp)_3$. The device consisting of a 2 % doped PVK furnished 4.5 % external quantum efficiency at 72 $cd/m^2$ (current density of 0.45 $mA/cm^2$ and drive voltage of 13.9 V) and a peak luminance of 25,000 $cd/m^2$ at 23.4 V (494 $mA/cm^2$). This work demonstrates the impact of the presence of a methyl substituent at the 3-position of the pyridyl ring of 2-phenylpyridine on the photophysical and electroluminescence properties.

• BMB Reports
• /
• v.35 no.4
• /
• pp.389-394
• /
• 2002

$[Ru(bpy)_2(dppz)]^2+$ (bpy=2,2'-bipyfidine, dppz=dipyrido[3,2-a:2',3'-c]phenazine) (RuBD), a long-lifetime metal-ligand complex, displays favorable photophysical properties. These include long lifetime, polarized emission, but no significant fluorescence from the complex that is not bound to DNA. To show the usefulness of this luminophore (RuBD) for probing the bending and torsional dynamics of nucleic acids, its intensity and anisotropy decays when intercalated into supercoiled and relaxed pTZ18U plasmids were examined using frequency-domain fluorometry with a blue light-emitting diode (LED) as the modulated light source. The mean lifetimes for the supercoiled plasmids (< $\tau$ >=148 ns) were somewhat shorter than those for the relaxed plasmids (< $\tau$ >=160 ns). This suggests that the relaxed plasmids were shielded more efficiently from water. The anisotropy decay data also showed somewhat shorter slow rotational correlation times for supercoiled plasmids (288 ns) than for the relaxed plasmids (355 ns). The presence of two rotational correlation times suggests that RuBD reveals both the bending and torsional motions of the plasmids. These results indicate that RuBD can be useful for studying both the bending and torsional dynamics of mucleic acids.

• Bulletin of the Korean Chemical Society
• /
• v.26 no.2
• /
• pp.201-214
• /
• 2005

We have designed and developed novel luminescent lanthanide complexes for advanced photonics applications. Lanthanide(III) ions (Ln$^{3+}$) were encapsulated by the luminescent ligands such as metalloporphyrins and naphthalenes. The energy levels of the luminescent ligands were tailored to maintain the effective energy transfer process from luminescent ligands to Ln$^{3+}$ ions for getting a higher optical amplification gain. Also, key parameters for emission enhancement and efficient energy transfer pathways for the sensitization of Ln$^{3+}$ ions by luminescent ligands were investigated. Furthermore, to enhance the optophysical properties of novel luminescent Ln$^{3+}$ complexes, aryl ether-functionalized dendrons as photon antennas have been incorporated into luminescent Ln$^{3+}$ complexes, yielding novel Ln(III)-cored dendrimer complex. The novel Ln(III)-cored dendrimer complex has much higher PL intensity than the corresponding simple complex, due to the efficient site-isolation effect. In this article, we will deal with recent progress in the synthesis and photophysical studies of inert and stable luminescent Ln$^{3+}$ complexes for advanced photonics applications. Also, our review will include the exploratory investigation of the key parameters for emission enhancement and the effective energy transfer pathways from luminescent ligands to Ln$^{3+}$ ions with Ln(III)-chelated prototype complexes.

• Journal of the Korean Society for Marine Environment & Energy
• /
• v.15 no.1
• /
• pp.47-53
• /
• 2012

As one of the methods for recycling the FRP from the waste ships, separation of roving layer from the mat has some merits in a sense of the eco-friendly and economical recycling process. Similar characteristics, however, between the roving and the mat even with different ratio of the resin and the glass and the thickness of the roving, much thinner than the mat, make the mechanically automatic differentiation difficult. In this study spectrochemical differentiation between the two layers has been made using boiling concentrated sulfuric acid, methanol and isopropanol solution saturated with KOH, or hydrogen fluoride (HF) solution. Furthermore efficiently coloring water-soluble dye following the HF treatment makes the roving layer more distinguishable photophysically. The layer differentiation and the automatic layer distraction move up the date of simple and automatic separation process for the waste FRP.

• Macromolecular Research
• /
• v.17 no.9
• /
• pp.672-681
• /
• 2009

A series of inert and photo-stable Er(III)-encapsulated complexes based on ${\pi}$-extended dendritic anthracene ligands bearing G3-aryl-ether dendron ([G3-AnX]-$CO_2H$), which retain different ${\pi}$-bridging systems, such as single (X= S), double (X= D) and triple (X= T) bonds was designed and synthesized to establish the structure-property relationship. The near infrared emission intensities of Er(III)-encapsulated complexes were enhanced dramatically by increasing the ${\pi}$-conjugated extension of anthracene ligands. The time-resolved luminescence spectra show monoexponential decays with a lifetime of $2.0{\sim}2.4ms$ for $Er^{3+}$ ions in thin films, and calculated intrinsic quantum yields of $Er^{3+}$ ions are in the range of $0.025{\sim}0.03%$. As a result, all Er(III)-encapsulated dendrimer complexes exhibit the near IR emission with the following order: $Er^{3+}-[G3-AnD]_3$(terpy) > $Er^{3+}-[G3-AnS]_3$(terpy) ${\approx}$ $Er^{3+}-[G3-AnT]_3$(terpy), because $Er^{3+}-[G3-AnD]_3$(terpy) has a higher relatively spectral overlap J value and energy transfer efficiency. In addition, the lack of detectable phosphorescence and no significant spectral dependence of the ${\pi}$-extended anthracene moieties on the solvent polarity support energy transfer from their singlet state to the central $Er^{3+}$ ion taking place in $Er^{3+}-[G3-AnX]_3$(terpy).

• Bulletin of the Korean Chemical Society
• /
• v.28 no.8
• /
• pp.1249-1255
• /
• 2007

We have investigated the photophysical properties of dansyl-N-methylaminobenzoic acid (DABAH) as a ligand and its lanthanide (Ln3+)-cored complexes (Ln3+-(DABA)3(terpy)) in order to determine the main energy transfer pathway for sensitized near infrared emission of Ln3+ ions (Ln3+ = Nd3+ and Er3+) in Ln3+- (DABA)3(terpy). The fluorescence spectrum of DABAH shows a large Stokes shift with increasing solvent polarity. This large Stokes shift might be due to the formation of a twisted intramolecular charge transfer (TICT) state, as demonstrated by the large dipole moment in the excited state. It is in good agreement with the result that the phosphorescence even in the Gd3+-cored complex based on the DABAH ligand was not observed, maybe due to the highly forbidden character of the S1 → T1 transition in the DABAH ligand. A short decay component (ca. 1 ns) was observed in Er3+-(DABA)3(terpy) whereas the fluorescence lifetimes of DABAH and its Gd3+-(DABA)3(terpy) are observed about ~10 ns. The short component could be originated from the energy transfer process between the ligand and the Ln3+ ion. Based on the fluorescence of DABAH its Ln3+- (DABA)3(terpy), the sensitization of Ln3+ luminescence in the Ln3+-(DABA)3(terpy) takes place by the energy transfer via the TICT state of DABAH in the excited singlet state rather than via the excited triplet state.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.11
• /
• pp.3645-3650
• /
• 2012

Two new blue emitting cationic iridium(III) complexes with two substituted 2-phenlypyridine ligands as main ligands and one 2,2'-biimidazole as an ancillary ligand, $[(L1)_2Ir(biim)]Cl$ (1) and $[(L2)_2Ir(biim)]Cl$ (2), where L1 = 2-(2',4'-difluorophenyl)-4-methylpyridine, L2 = 2-(2',4'-difluoro-3'-trifluoromethylphenyl)-4-methylpyridine and biim = 2,2'-biimidazole, were synthesized for applications in phosphorescent organic light-emitting diodes (PhOLEDs). Their photophysical, electrochemical and electroluminescent (EL) device performances were examined. The photoluminescent (PL) spectra revealed blue phosphorescence in the 450 to 485 nm range with a quantum yield of more than 10%. The iridium(III) compounds studied showed good solubility in organic solvents with no solvatochromism dependent on the solvent polarity. The solution-processed OLEDs were prepared with the configuration, ITO/PEDOT:PSS (40 nm)/mCP:Ir(III) (70 nm)/OXD-7 (20 nm)/LiF (1 nm)/Al (100 nm), by spin coating the emitting layer containing the mCP host doped with the iridium phosphors. The best performance of the fabricated OLEDs based on compound 1 showed an external quantum efficiency of 4.5%, luminance efficiency of 8.52 cd $A^{-1}$ and blue emission with the CIE coordinates (x,y) of (0.16, 0.33).

• Bulletin of the Korean Chemical Society
• /
• v.30 no.7
• /
• pp.1553-1558
• /
• 2009

A series of Eu(III) complexes with various neutral ligands (2,2’:6’,2"-terpyridine (T), diglyme (D), 1N-(2-dimethylamino) ethyl)-1N, 2N, 2N-trimethylethane-1,2-diamine (PT), di-(2-picolyl)-amine derivative (HT), and multidentate terpyridine derivative (DT)) were synthesized to investigate the effect of coordination environment on the sensitized luminescence of Eu(III) complexes. The nine coordination sites of the $Eu^{3+}$ ion are occupied by three bidentate carboxylate moieties and one neutral ligand. The highest emission intensity is obtained for $Eu^{3+}$- $[NA]_3$ (PT), due to the difference in energy transfer efficiency and symmetry of the first coordination sphere of $Eu^{3+}$ ion. But, the lowest emission intensity is obtained for $Eu^{3+}$-$[NA]_3$(T). Terpyridine may not play an important role antenna for photosensitizing $Eu^{3+}$ ion. It could be attributed to the weak spectral overlap integral J value between its phosphorescence band and $Eu^{3+}$ion absorption band. Therefore, different coordination environment of $Ln^{3+}$ ion play an important role in providing sensitization of lanthanide ion emission.

• Macromolecular Research
• /
• v.12 no.3
• /
• pp.282-289
• /
• 2004

We have extensively characterized the fluorescence behavior of unsaturated polyester (UP) resin in the absence and presence of a 1,3-bis-(l-pyrenyl)propane (BPP) fluorescent probe at various dynamic and isothermal cure histories by means of a steady-state fluorescence technique using a front-face illumination equipment. In addition, we explored the effect of the fluorescence intensity on the relaxation of the fluorescent probe in the UP resin by resting the dynamically and isothermally cured resin at ambient temperature and pressure for 24 h. The monomer fluorescence intensity, which has two characteristic peaks at 376 and 396nm, changed noticeably depending on the cure temperature and time and provided important information with respect to the molecular and photophysical responses upon curing. The result of the fluorescence study indicates that the increased local viscosity and restricted molecular mobility of the UP resin surrounding the BPP probe after curing are both responsible for the enhancement of the monomer fluorescence intensity. Our results also demonstrate that once the BPP probe has enough time to rearrange and become isolated prior to fluorescence, a sufficient amount of fluorescence is emitted. Therefore, we note that the fluorescence behavior of this UP resin system is influenced strongly by the relaxation process of the fluorescent probe in the resin as well as process used to cure the resin.