• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4321-4326
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• 2011

A new series of heteroleptic cyclometalated iridium(III) complexes has been synthesized and characterized by absorption, emission and cyclic voltammetry studies: $(pqx)_2Ir(acac)$ (1), $(dmpqx)_2Ir(acac)$ (2) and $(dfpqx)_2Ir(acac)$ (3) where pqx=2-phenylquinoxalinate, dmpqx=2-(2,4-dimethoxyphenyl)quinoxalinate, dfpqx=2-(2,4-difluorophenyl) quinoxalinate and acac=acetylacetonate anion. The reaction of excess acetylacetone with ${\mu}$-chloride-bridged dimeric iridium complex, $[(C\^N)_2Ir({\mu}-Cl)]_2$, gives a complex 1 and an unusual hydridoiridium(III) complex, $(pqx)IrH(acac)_2$ (4). The complex 1, 2 and 3 show their emissions in an orangered region (${\lambda}_{PL,max}$ = 583-616 nm), and the emission maxima can be tuned by the change of substituent at phenyl ring of 2-phenylquinoxaline ligand. The phosphorescent line shape indicates that the emissions originate predominantly from $^3MLCT$ states with little admixture of ligand-based $^3({\pi}-{\pi}^*)$ excited states. The structures of complex 3 and 4 are additionally characterized by a single crystal X-ray diffraction method. The complex 3 shows a distorted octahedral geometry around iridium(III) metal ion. A strong trans influence of the phenyl ring is examined. In complex 4, there are two discrete molecules which are mirror images each other at the ratio of 1:1 in an unit cell. We propose that the phosphorescent complex 1, 2 and 3 are possible candidates for the phosphors in OLEDs applications.

• Bulletin of the Korean Chemical Society
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• 제28권10호
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• pp.1860-1862
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• 2007

• Bulletin of the Korean Chemical Society
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• 제31권12호
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• pp.3711-3717
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• 2010

Four orange-red phosphorescent Ir(III) complexes were designed and synthesized based on the benzoylphenylpyridine ligand with a fluorine substituent. Multilayered OLEDs with the device structure, ITO/2-TNATA/NPB/CBP : 8% Ir(III) complexes/BCP/Liq/Al, were fabricated using these complexes as dopant materials. All the devices exhibited orange-red electroluminescence and their electroluminescent properties were quite sensitive to the structural features of the dopants in the emitting layers. Among these, the maximum luminance ($14700\;cd/m^2$ at 14.0 V) was observed in the device containing Ir(III) complex 1 as the dopant. In addition, its luminous, power and quantum efficiency were 11.7 cd/A, 3.88 lm/W and 9.58% at $20\;mA/cm^2$, respectively. The peak wavelength of electroluminescence was 606 nm with CIE coordinates of (0.61, 0.38) at 12.0 V. The device also showed stable color chromaticity with various voltages.

• Bulletin of the Korean Chemical Society
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• 제35권11호
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• pp.3199-3204
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• 2014

Two novel phosphorescent heteroleptic cationic Ir(III) complexes, Ir(bt)2(dmpe) (Ir1) and Ir (bt)2(dppe) (Ir2), where bt is 2-phenylbenzothiazole, dmpe is 1,2-bis(dimethylphosphino)ethane, and dppe is 1,2-bis(diphenyl-phosphino) ethane, were designed and synthesized. Their photophysical and electrochemical properties and the X-ray structure of the Ir1 complex were investigated. The prepared Ir(III) complexes exhibited blue-green emissions at 503-538 nm with vibronic fine structures in dichloromethane solution and PMMA film, implying that the lowest excited states are dominated by ligand-based $^3{\pi}-{\pi}^*$ transitions. The ${\pi}$-acceptor ability of the diphosphine ancillary ligand leads to blue-shift emission. The room temperature photoluminescent quantum yields (PLQYs) of Ir1 and Ir2 were 52% and 45%, respectively, in dichloromethane solution. These high PLQYs resulted from steric hindrances by the bulky cationic iridium complexes. The crystal structure of Ir1 was determined by X-ray crystallography, which revealed that central iridium adopted a distorted octahedral structure coordinated with two bt ligands (N^C) and one dmpe ligand (P^P) showing cis C-C and trans N-N dispositions. The bent nature of the dmpe ligand resulted in a relatively wide bite angle of $83.83^{\circ}$ of P-Ir-P.

• Bulletin of the Korean Chemical Society
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• 제25권10호
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• pp.1503-1507
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• 2004

New synthetic methodology of the saturated and unsaturated Er(III)-chelated prototype complexes based on benzoate and pentafluorobenzoate ligands was developed through ligand-exchange reaction. The saturated 8-coordinated Er(III) complexes exhibit stronger near-IR emission than those of the unsaturated 6-coordinated Er(III) complexes, obtained from the direct photoexcitation of Er ions with 488 nm. Three $H_2O$ molecules coordinated in the unsaturated 6-coordinated complexes seriously quenched the near IR emission by the harmonic vibration relaxation decay of O-H bonds. Also, the stronger emission of the Er(III) complexes was obtained by the indirect photoexcitation of ligands than by the direct photoexcitation of the Er(III) ions, due to the energy transfer between the excited ligand and the erbium ion. Furthermore, the saturated Er(III)-chelated complex with C-F bonds shows much stronger near IR emission than that of the saturated Er(III)-chelated complex with C-H bonds. It is attributed to the influence of C-F bonds on near IR emission.

• Korean Chemical Engineering Research
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• 제49권3호
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• pp.325-329
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• 2011

본 연구를 통해 최근 개발된 근자외선영역대에서 발광하는 이리듐 착물인 $Ir(pmb)_{3}$ (Iridium(III) Tris(1-phenyl-3-methylbenzimidazolin-2-ylidene-C,$C,C^{2'}$ ))의 합성 과정상에서 기존의 합성법과 동일한 발광 특성을 가지면서 더 효율적인 합성 방법을 제안하였다. 합성 과정에서 초음파가 투입되면서 용매에 녹지 않는 반응물의 파쇄 및 혼합을 돕고, 촉매의 활성을 향상시켜 이온 및 라디컬을 형성시키는 방법으로 최대 42.5% 합성 수율을 얻어 내었으며 이는 기존 방법 대비 약 4배 이상 향상된 결과이다. 이러한 초음파 합성법으로 합성된 $Ir(pmb)_{3}$은 이성질체 별로 405 nm(면이성질체) 412 nm(자오선이성질체)의 발광 피크를 보였으며 이중 좀더 효율이 높은 자오선이성질체를 사용하여 전계 발광 소자를 제작하였다. 밴드갭이 큰 $Ir(pmb)_{3}$에 적합한 호스트 물질을 UGH2, CBP, mCP 세가지 선정하여 전계발광소자를 제작하였으며, 그 중 mCP를 호스트 물질로 사용한 소자의 경우가 호스트물질과 인광물질사이의 에너지전달이 가장 효율적으로 일어나 가장 높은 휘도와 효율을 보였다.

• Bulletin of the Korean Chemical Society
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• 제31권8호
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• pp.2309-2314
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• 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
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• 제3권1호
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• pp.6-10
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• 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.

• 대한화학회지
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• 제29권3호
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• pp.247-251
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• 1985

네자리 리간드인 ethylenediamine-N,N'-di-S-${\alpha}$-propionic acid (eddp)의 디클로로 코발트(III) 착물을 공기산화법에 의하여 합성하였다. eddp리간드는 코발트(III) 이온에 매우 입체선택적으로 배위하여 ${\Delta}$-S-cis 이성체만을 형성함이 관찰되었다. 합성된 착물의 구조는 원소분석, 적외선 분광분석법, 핵자기 공명 및 흡수스펙트럼으로 확인되었으며 특히 착물의 절대배열은 핵자기공명 스펙트럼으로 확인하였다.

• 대한화학회지
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• 제22권1호
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• pp.25-29
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• 1978

수용액 중에서 ethylenediamine-tetraacetatocobaltate(III) 錯物에 트리메틸렌디아민(tn)을 반응시켜 얻어지는 [Co(tn)(HEDTRA)]Cl${\cdot}$2$H_2O$ 錯物을 수소이온형 陽이온교환수지, Dowex 50WX8을 이용하여 분리하였다. $EDTRA^{3-}$(ethylenediamine-triacetate) 리간드는 유리 식초산 가지를 갖고 4자리 형태로 코발트(III) 이온에 배위되어 있으며, 원소분석, UV, IR, NMR 등 분광학적 방법을 이용하여 얻어진 錯物은 가능한한 기학적 이성질체 중에서 trans(O-O)(1) 형태의 구조를 가지고 있음을 확인하였다.