• Title/Summary/Keyword: MLCT spectrum

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Polymer Phosphorescence Device using a New Green Emitting Ir(III) Complex

  • Lee, Chang-Lyoul;Das, Rupasree Ragini;Noh, Yong-Young;Kim, Jang-Joo
    • Journal of Information Display
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    • v.3 no.1
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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.

Determination of inclusion complex formation constants for the β-CD and [Cu(Dien)(sub-Py)]2+ ion by the spectrophotometric methods (분광 광도법에 의한 β-CD와 [Cu(Dien)(sub-Py)]2+이온간의 복합체 형성 상수 결정)

  • Kim, Chang Suk;Oh, Ju Young
    • Analytical Science and Technology
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    • v.20 no.5
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    • pp.406-412
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    • 2007
  • The formation of inclusion complexes between ${\beta}$-cyclodextrin and diethylenetriamine substituted-pyridine copper(II) perchlorate; [Cu(dien)(sub-py)] $(ClO_4)_2$, were studied by spectrophotometric methods. On account of charge-transfer band(MLCT) and $^2T_2{\rightarrow}^2E$, the two high peaks were observed as an inclusion complex for the [${\beta}$-CD]$[Cu(dien)(p-Cl-py)]^{2+}$ in the ultraviolet region of the spectrum. The ${\beta}$-CD and $[Cu(dien)(sub-py)]^{2+}$ ion formed a 1:1 complex, and the formation constants were decreased with the increasing temperatures, due to weak binding energy between ${\beta}$-CD and $[Cu(dien)(sub-py)]^{2+}$ ion. This reaction was controlled by enthalpy. In a correlation of the Hammett substituent constants and formation constants for the reaction, formation constants were increased by strong binding energy in the inclusion complexes when electron donating groups were substituted in pyridine ring.

Studies on the Electrochemical Behaviors, Spectrophotometric Determination of Heavy Lanthanide Ions and Heavy Metal Chelate Complexes with Bidentate Ligands(III) -Synthesis and Characterization of the Tetrakis(5,7-dichloro-8-quinolinato)(2-mercaptopyrimidinato) molybdenum(IV) Complex- (무거운 란탄이온의 전기화학적 거동, 분광학적 정량 및 중금속 이온과 두 자리 리간드 착물에 관한 연구(제 3 보): -테트라키스(5,7-디클로로-8-퀴놀리나토)(2-메르캅토피리미디나토) 몰리브데늄(IV) 착물의 합성 및 특성-)

  • Chang, Choo Hwan;Choi, Won Jong;Park, Keun Su;Son, Pyung Su;Suh, Moo Yul
    • Analytical Science and Technology
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    • v.6 no.5
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    • pp.417-424
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    • 1993
  • Eight-coordinate tetrakis molybdenum(IV) complexes containing 5,7-dichloro-8-hydroxyquinolinol(Hdcq) and 2-mercaptopyrimidine(Hmpd) has been prepared. $Mo(mpd)_4$, $Mo(dcq)(mpd)_3$, $Mo(dcq)_2(mpd)_2$, $Mo(dcq)_3(mpd)$ and $Mo(dcq)_4$ complexes have been isolated by thin-layer chromatography on silicagel plates. These complexes have been charaterized by $^1H-nmr$ spectrum and UV-Vis. spectrum. The chemical shift values of the protons ${\alpha}$ to the nitrogen in the ligands are shifted to down field. The relative intensities of the peaks which are positioned at the same proton of $Mo(dcq)(mpd)_3$ and $Mo(dcq)_3(mpd)$ are observed in 2:1 ratio, in case of $Mo(dcq)_2(mpd)_2$ appears in approximately a 1:1 ratio. The stereochemistry of the complexes in discussed in terms of their nmr spectrum and Orgel's rule. By vertue of the intensities (${\varepsilon}$>10,000~25,000) the low energy($16,600{\sim}19,800cm^{-1}$) bands are observed for the electronic spectra of the complexes are assigned as charge transfer bands.

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Unidirectional Photo-induced Charge Separation and Thermal Charge Recombination of Cofacially Aligned Donor-Acceptor System Probed by Ultrafast Visible-Pump/Mid-IR-Probe Spectroscopy

  • Kim, Hyeong-Mook;Park, Jaeheung;Noh, Hee Chang;Lim, Manho;Chung, Young Keun;Kang, Youn K.
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.587-596
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    • 2014
  • A new ${\pi}$-stacked donor-acceptor (D-A) system, [Ru(1-([2,2'-bipyridine]-6-yl-methyl)-3-(2-cyclohexa-2',5'-diene-1,4-dionyl)-1H-imidazole)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (ImQ_T), has been synthesized and characterized. Similar to its precedent, [Ru(6-(2-cyclohexa-2',5'-diene-1,4-dione)-2,2':6',2"-terpyridine)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (TQ_T), this system has a cofacial alignment of terpyridine (tpy) ligand and quinonyl (Q) group, which facilitates an electron transfer through ${\pi}$-stacked manifold. Despite the presence of lowest-energy charge transfer transition from the Ru-based-HOMO-to-Q-based-LUMO (MQCT) predicted by theoretical calculations by using time-dependent density functional theory (TD-DFT), the experimental steady-state absorption spectrum does not exhibit such a band. The selective excitation to the Ru-based occupied orbitals-to-tpy-based virtual orbital MLCT state was thus possible, from which charge separation (CS) reaction occurred. The photo-induced CS and thermal charge recombination (CR) reactions were probed by using ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. Analysis of decay kinetics of Q and $Q^-$ state CO stretching modes as well as aromatic C=C stretching mode of tpy ligand gave time constants of <1 ps for CS, 1-3 ps for CR, and 10-20 ps for vibrational cooling processes. The electron transfer pathway was revealed to be Ru-tpy-Q rather than Ru-bpy-imidazol-Q.