• 제목/요약/키워드: Metal complexes

검색결과 666건 처리시간 0.025초

란탄계 금속 착화합물을 이용한 다양한 유기 전기 발광 소자의 연구 (A Study on the Various Organic Electroluminescent Devices Using Lanthanide Chelate Metal Complexes)

  • 표상우;이한성;김정수;이승희;김영관
    • 한국전기전자재료학회:학술대회논문집
    • /
    • 한국전기전자재료학회 1999년도 추계학술대회 논문집
    • /
    • pp.529-532
    • /
    • 1999
  • 본 연구에서는 유기 전기 발광 소자에서 녹색 발광층으로 사용되는 terbium(Tb) complexes와 europium(Eu) complex, 정공 수송층으로 사용되는 TPD (N, N\`-diphenyl-N,\`(3-methylphenyl)-1, 1\`biphenyl-4, 4\`-diamine), 그리고 전자 수송층으로 사용되는 Alq$_{3}$ (trois(8-hydroxyquinolino)aluminum), Bebq$_2$들의 Uv/Vis. 홉광도와 PL 스펙 트럼과 같은 광학적 특성을 조사하였으며 또한 이러한 물질들을 이용하여 다양한 종류의 유기 전기 발광 소자를 제작하고 제작된 소자들의 전류밀도-전압-조도 등의 전기 . 광학적 특성을 조사하였으며, 그 결과 다 음과 같은 결곤을 얻을 수 있었다. 다양한 ligand를 갖는 Tb complex들의 경우에도 EL 스펙트럼의 파장대 (wavelength)는 546nm~548nm의 녹색 발광을 하는 것을 알 수 있었고, 제작된 소자 중에서 Tb(ACAC)$_3$(Phen) 을 발광충으로 하고, TPD, 그리고 Bebq$_2$를 각각 정공 수송층, 전자 수송 층으로 한 소자가 가장 낮은 구동 전압을 갖는다는 것을 확인하였으며 logJ-logV 특성에서도 모든 전계 구간에서 이러한 구조의 소자가 가장 높은 전류밀도를 나타냈으며 저 전계 구간에서 전류밀도 타이가 가장 컸다. 소자의 전류밀도와 휘도의 관계에 있어서는 제작된 네 종류의 소자 중 Tb(ACAC)3(Cl-Phen)를 발광층으로 하고 TPD, 그리고 Bebq2를 각각 정공 수송층, 전자 수송 층으로 한 소자가 가장 휘도가 우수한 것을 알 수 있었다. 또한 red (europium complex), green (terbium complex), 그리고 blue (TPD) 색깔을 나타내는 유기 재료를 사용하여 한 소자에서 백색 소자를 제작하여 cyclic voltametric방법을 이용하여 각 유기 물질들의 에너지 준위를 조사하여, 각각의 소자들을 에너지 밴드 다이어그램(energy band diagram)으로 자세히 설명하였다.

  • PDF

New Transition Metal Mediated Alkylation Reaction of arachno-$S_{2}B_{7}H_{8}$, Insertion Reaction of arachno-$S_{2}B_{7}H_{8}^{-}$ with $(CO)_{5}M$ {${C(R_{1})(R_{2})}$} $(M=Cr,\;W;\;R_{1}=CH_{3},\;C_{6}H_{5};\;R_{2}=OCH_{3},\;SC_{6}H{5})$: Synthesis and Characterization of arachno-$4-RCH_{2}-6,8-S_{2}B_{7}H_{8}\;(R=CH_{3},\;IIa;\;C_{6}H_{5},\;IIb)$

  • Hee-Joo Jeon;Jae-Jung Ko;Kang-bong Lee;Sang Ook Kang
    • Bulletin of the Korean Chemical Society
    • /
    • 제14권1호
    • /
    • pp.113-117
    • /
    • 1993
  • Good yield synthetic routes for the production of new B-alkyl-dithiaborane clusters are reported. The syntheses of the B-alkyl-dithiaboranes are based on the use of Fischer-type carbene reagents to activate the B-H bonds of dithiaborane for alkyl-addition reactions and are the first examples of transition-mediated reactions of dithiaborane to be reported. Thus, reactions employing arachno-$S_2B_7H_8$- and $(CO)_5M{C(R_1)R_2}$ (M = Cr, W; $R_1 = CH_3,\;C_6H_5;\; R_2 = OCH_3,\;SC_6H_5)$ were found to yield the intermidiate anions I, $[(CO)_5M{C(R_1)R_2S_2B_7H_8}]^-$, which upon protonation gave the corresponding neutral, air-sensitive cluster arachno-4-$RCH_2-6,8-S_2B_7H_8(R=CH_3,\;IIa;\;C_6H_5,\;IIb)$ range from 30 to 35% yield. Complexes IIa and IIb are isoelectronic with arachno-6,8-$S_2B_7H_9$ and, on the basis of the spectroscopic data, are proposed to adopt a similar arachno cage geometry in which an $RCH_2$ units are substituted to 4 position boron atom of the arachno-6,8-$S_2B_7H_9$.

A New Functional Model of Catechol Dioxygenases: Properties and Reactivity of [Fe(BLPA)DBC]$BPh_4$

  • Lim, Ji H.;Lee, Ho J.;이강봉;Jang, Ho G.
    • Bulletin of the Korean Chemical Society
    • /
    • 제18권11호
    • /
    • pp.1166-1172
    • /
    • 1997
  • [FeⅢ(BLPA)DBC]BPh4, a new functional model for the catechol dioxygenases, has been synthesized, where BLPA is bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine and DBC is 3,5-di-tert-butylcatecholate dianion. The BLPA complex has a structural feature that iron center has a six-coordinate geometry with N4O2 donor set. It exhibits EPR signals at g=5.5 and 8.0 which are typical values for the high-spin FeⅢ (S=5/2) complex with axial symmetry. The BLPA complex reacts with O2 within a few hours to afford intradiol cleavage (75%) and extradiol cleavage (15%) products which is very unique result of all [Fe(L)DBC] complexes studied. The iron-catecholate interaction of BLPA complex is significantly stronger, resulting in the enhanced covalency of the metal-catecholate bonds and low energy catecholate to FeⅢ charge transfer bands at 583 and 962 nm in CH3CN. The enhanced covalency is also reflected by the isotropic shifts exhibited by the DBC protons, which indicate increased semiquinone character. The greater semiquinone character in the BLPA complex correlates well with its high reactivity towards O2. Kinetic studies of the reaction of the BLPA complex with 1 atm O2 in CH3OH and CH2Cl2 under pseudo-first order conditions show that the BLPA complex reacts with O2 much slower than the TPA complex, where TPA is tris(2-pyridylmethyl)amine. It is presumably due to the steric effect of the methyl substituent on the pyridine ring. Nevertheless, both the high specificity and the fast kinetics can be rationalized on the basis of its low energy catecholate to FeⅢ charge transfer bands and large isotropic NMR shifts for the BLPA protons. These results provide insight into the nature of the oxygenation mechanism of the catechol dioxygenases.

Pt/CNT 전극 기반 전기화학식 센서의 전해질에 따른 황화수소 감지 특성 (Hydrogen Sulfide Sensing Characteristics Depending on Electrolytes of Pt/CNT Liquid Electrochemical Sensors)

  • 하윤태;권진범;최수지;백수빈;정대웅
    • 센서학회지
    • /
    • 제32권3호
    • /
    • pp.194-198
    • /
    • 2023
  • With the recent development of industrial technology, the problem of odor due to leakage of toxic gas discharged from industrial complexes is gradually increasing. Among them, hydrogen sulfide is a colorless representative odorous substance that can cause pain through irritation of the mucous membranes of the eyes and respiratory tract, and is a gas that can cause central nervous system paralysis and suffocation when exposed to high concentrations. Therefore, in order to improve the odor problem, research on a gas sensor capable of quickly and reliably detecting a leak of hydrogen sulfide is being actively conducted. A lot of research has been done on the existing metal oxide-based hydrogen sulfide gas sensor, but it has the disadvantage of requiring low selectivity and high temperature operating conditions. Therefore, in this study, a Pt/CNT-based electrochemical hydrogen sulfide gas sensor capable of detecting at low temperatures with high selectivity for hydrogen sulfide was developed. A working electrode capable of selectively detecting only hydrogen sulfide was fabricated by synthesizing Pt nanoparticles as a catalyst on functionalized CNT and applied to an electrochemical hydrogen sulfide gas sensor. It was confirmed that the manufactured Pt/CNT-based electrochemical hydrogen sulfide gas sensor has a current change of up to 100uA for hydrogen sulfide, and the both response time and recovery time were within 15 seconds.

전이금속 이온과 Macrocyclic Ligand 사이의 반응에 관한 속도론적 연구 질소원자와 산소원자를 포함하는 거대고리 리간드를 중심으로 (Kinetic Studies of Reaction of Transion Metal Ion with Macrocyclic Ligands. Containing Nitrogen and Oxygen Donor Atoms)

  • 김진호;조문환;현동호;박휴범;김시중;이인종
    • 대한화학회지
    • /
    • 제34권5호
    • /
    • pp.418-423
    • /
    • 1990
  • 새로이 합성된 거대고리 리간드 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloeicosane (NdienOdienH$_4$)와 이미 합성된 거대고리 리간드 1,12,15-triaza-3,4;9,10-dibenzo-5,8-dioxa cycloheptadecane (NdienOenH$_4$)와 1,15-diaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloheptadecane (NenOdienH$_4$)를 25$^{\circ}C$ 수용액에서 전위차계를 이용하여 양성자 첨가반응의 평형상수를 구하였다. 또한 위의 세 가지 리간드 각각과 Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ)의 금속이온과의 착물을 합성하여 25$^{\circ}C$수용액에서 안정도 상수를 전위차법으로 구하였다. 그리고 위의 착물 수용액에 에틸렌 디아민용액을 가해 착물의 리간드 치환반응 속도상수를 분광광도법으로 측정하였다. 그리고 활성화에너지와 활성화파라메타(${\{Delta}H^{\neq}$, ${\{Delta}S^{\neq}$)를 구하여 이 반응계의 타당한 메카니즘을 제안하였다.

  • PDF

염료감응형 광전기화학 물분해 전지용 Tri-branched tri-anchoring organic dye 개발 (Tri-branched tri-anchoring organic dye for Visible light-responsive dye-sensitized photoelectrochemical water-splitting cells)

  • 박정현;김재홍;안광순
    • 한국신재생에너지학회:학술대회논문집
    • /
    • 한국신재생에너지학회 2010년도 춘계학술대회 초록집
    • /
    • pp.87-87
    • /
    • 2010
  • Photoelectrochemical (PEC) systems are promising methods of producing H2 gas using solar energy in an aqueous solution. The photoelectrochemical properties of numerous metal oxides have been studied. Among them, the PEC systems based on TiO2 have been extensively studied. However, the drawback of a PEC system with TiO2 is that only ultraviolet (UV) light can be absorbed because of its large band gap (3.2 - 3.4 eV). Two approaches have been introduced in order to use PEC cells in the visible light region. The first method includes doping impurities, such as nitrogen, into TiO2, and this technique has been extensively studied in an attempt to narrow the band gap. In comparison, research on the second method, which includes visible light water splitting in molecular photosystems, has been slow. Mallouk et al. recently developed electrochemical water-splitting cells using the Ru(II) complex as the visible light photosensitizer. the dye-sensitized PEC cell consisted of a dye-sensitized TiO2 layer, a Pt counter electrode, and an aqueous solution between them. Under a visible light (< 3 eV) illumination, only the dye molecule absorbed the light and became excited because TiO2 had the wide band gap. The light absorption of the dye was followed by the transfer of an electron from the excited state (S*) of the dye to the conduction band (CB) of TiO2 and its subsequent transfer to the transparent conducting oxide (TCO). The electrons moved through the wire to the Pt, where the water reduction (or H2 evolution) occurred. The oxidized dye molecules caused the water oxidation because their HOMO level was below the H2O/O2 level. Organic dyes have been developed as metal-free alternatives to the Ru(II) complexes because of their tunable optical and electronic properties and low-cost manufacturing. Recently, organic dye molecules containing multi-branched, multi-anchoring groups have received a great deal of interest. In this work, tri-branched tri-anchoring organic dyes (Dye 2) were designed and applied to visible light water-splitting cells based on dye-sensitized TiO2 electrodes. Dye 2 had a molecular structure containing one donor (D) and three acceptor (A) groups, and each ended with an anchoring functionality. In comparison, mono-anchoring dyes (Dye 1) were also synthesized. The PEC response of the Dye 2-sensitized TiO2 film was much better than the Dye 1-sensitized or unsensitized TiO2 films.

  • PDF

카바졸과 페노시아진을 이용한 염료감응형 태양전지의 염료 합성과 광적특성 (Synthesis and Photovoltaic Properties of Dendritic Photosensitizers containing Carbazole and Phenothiazine for Dye-sensitized Solar Cells)

  • 김명석;정대영;김재홍
    • 한국신재생에너지학회:학술대회논문집
    • /
    • 한국신재생에너지학회 2010년도 춘계학술대회 초록집
    • /
    • pp.89.1-89.1
    • /
    • 2010
  • Since Gratzel and co-workers developed a new type of solar cell based on the nanocrystalline $TiO_2$ electrode, dye-sensitized solar cells (DSSCs) have attracted considerable attention on account of their high solar energy-to-conversion efficiencies (11%), their easy manufacturing process with low cost production compared to conventional p-n junction solar cells. The mechanism of DSSC is based on the injection of electrons from the photoexcited dye into the conduction band of nanocrystalline $TiO_2$. The oxidized dye is reduced by the hole injection process from either the hole counter or electrolyte. Thus, the electronic structures, such as HOMO, LUMO, and HOMO-LUMO gap, of dye molecule in DSSC are deeply related to the electron transfer by photoexcitation and redox potential. To date, high performance and good stability of DSSC based on Ru-dyes as a photosensitizer had been widely addressed in the literatures. DSSC with Ru-bipyridyl complexes (N3 and N719), and the black ruthenium dye have achieved power conversion efficiencies up to 11.2% and 10.4%, respectively. However, the Ru-dyes are facing the problem of manufacturing costs and environmental issues. In order to obtain even cheaper photosensitizers for DSSC, metal-free organic photosensitizers are strongly desired. Metal-free organic dyes offer superior molar extinction coefficients, low cost, and a diversity of molecular structures, compared to conventional Ru-dyes. Recently, novel photosensitizers such as coumarin, merocyanine, cyanine, indoline, hemicyanine, triphenylamine, dialkylaniline, bis(dimethylfluorenyl)-aminophenyl, phenothiazine, tetrahydroquinoline, and carbazole based dyes have achieved solar-to-electrical power conversion efficiencies up to 5-9%. On the other hand, organic dye molecules have large ${\pi}$-conjugated planner structures which would bring out strong molecular stacking in their solid-state and poor solubility in their media. It was well known that the molecular stacking of organic dyes could reduce the electron transfer pathway in opto-electronic devices, significantly. In this paper, we have studied on synthesis and characterization of dendritic organic dyes with different number of electron acceptor/anchoring moieties in the end of dendrimer. The photovoltaic performances and the incident photon-to-current (IPCE) of these dyes were measured to evaluate the effects of the dendritic strucuture on the open-circuit voltage and the short-circuit current.

  • PDF

multi-chromophore를 가지는 유기염료의 DSSC 광전변환거동 (Photovoltaic Properties of Dendritic Photosensitizers containing multi-chromophore for Dye-sensitized Solar Cells)

  • 김명석;천종훈;정대영;김재홍
    • 한국신재생에너지학회:학술대회논문집
    • /
    • 한국신재생에너지학회 2011년도 춘계학술대회 초록집
    • /
    • pp.117.2-117.2
    • /
    • 2011
  • Since Gratzel and co-workers developed a new type of solar cell based on the nanocrystalline TiO2 electrode, dye-sensitized solar cells (DSSCs) have attracted considerable attention on account of their high solar energy-to-conversion efficiencies (11%), their easy manufacturing process with low cost production compared to conventional p-n junction solar cells. The mechanism of DSSC is based on the injection of electrons from the photoexcited dye into the conduction band of nanocrystalline TiO2. The oxidized dye is reduced by the hole injection process from either the hole counter or electrolyte. Thus, the electronic structures, such as HOMO, LUMO, and HOMO-LUMO gap, of dye molecule in DSSC are deeply related to the electron transfer by photoexcitation and redox potential. To date, high performance and good stability of DSSC based on Ru-dyes as a photosensitizer had been widely addressed in the literatures. DSSC with Ru-bipyridyl complexes (N3 and N719), and the black ruthenium dye have achieved power conversion efficiencies up to 11.2% and 10.4%, respectively. However, the Ru-dyes are facing the problem of manufacturing costs and environmental issues. In order to obtain even cheaper photosensitizers for DSSC, metal-free organic photosensitizers are strongly desired. Metal-free organic dyes offer superior molar extinction coefficients, low cost, and a diversity of molecular structures, compared to conventional Ru-dyes. Recently, novel photosensitizers such as coumarin, merocyanine, cyanine, indoline, hemicyanine, triphenylamine, dialkylaniline, bis(dimethylfluorenyl)-aminophenyl, phenothiazine, tetrahydroquinoline, and carbazole based dyes have achieved solar-to-electrical power conversion efficiencies up to 5-9%. On the other hand, organic dye molecules have large ${\pi}$-conjugated planner structures which would bring out strong molecular stacking in their solid-state and poor solubility in their media. It was well known that the molecular stacking of organic dyes could reduce the electron transfer pathway in opto-electronic devices, significantly. In this paper, we have studied on synthesis and characterization of dendritic organic dyes with different number of electron acceptor/anchoring moieties in the end of dendrimer. The photovoltaic performances and the incident photon-to-current (IPCE) of these dyes were measured to evaluate the effects of the dendritic strucuture on the open-circuit voltage and the short-circuit current.

  • PDF

Polymerization of Hydrosilanes and Vinyl Monomers in the Presence of Transition Metal Complex

  • Kim, Myoung-Hee;Lee, Jun;Cha, Hyo Chang;Shin, Joong-Hyeok;Woo, Hee-Gweon
    • 통합자연과학논문집
    • /
    • 제2권1호
    • /
    • pp.18-23
    • /
    • 2009
  • This minireview provides the chosen examples of our recent discoveries in the polymerization of hydrosilanes, dihydrosilole, lactones, and vinyl derivatives using various catalysts. Hydrosilanes and lactones copolymerize to give poly(lactone-co-silane)s with $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) catalyst. Hydrosilanes (including dihydrosilole) reduce noble metal complexes (e.g., $AgNO_3$, $Ag_2SO_4$, $HAuCl_4$, $H_2PtCl_6$) to give nanoparticles along with silicon polymers such as polysilanes, polysilole, polysiloxanes (and silicas) depending on the reaction conditions. Interestingly, phenylsilane dehydrocoupled to polyphenylsilane in the inert nitrogen atmosphere while phenylsilane dehydrocoupled to silica in the ambient air atmosphere. $Cp_2M/CX_4$ (M = Fe, Co, Ni; X = Cl, Br, I) combination initiate the polymerization of vinyl monomers. In the photopolymerization of vinyl monomers using $Cp_2M/CCl_4$ (M = Fe, Co, Ni), the photopolymerization of MMA initiated by $Cp_2M/CCl_4$ (M = Fe, Co, Ni) shows while the polymerization yield decreases in the order $Cp_2Fe$ > $Cp_2Ni$ > $Cp_2Co$, the molecular weight decreases in the order $Cp_2Co$ > $Cp_2Ni$ > $Cp_2Fe$. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. The photopolymerizations are not living. Many exciting possibilities remain to be examined and some of them are demonstrated in the body of the minireview.

  • PDF

이온선택성 크라운 에테르 염료에 관한 연구 (Studies on Ion-Selective Crown Ether Dyes)

  • 강삼우;박종민;구원회;김근재;이수민;장주환
    • 대한화학회지
    • /
    • 제32권5호
    • /
    • pp.443-451
    • /
    • 1988
  • Monobenzo-15-crown-5와 Dibenzo-18-crown-6을 모체로 아조(-N=N-)기가 치환된 두가지 새로운 crown ether dye-Ⅰ과 dye-Ⅱ를 합성하여 스펙트럼을 조사한바 ${\lambda}_{max}$는 377nm 와 383nm에서 나타났고. 이 crown ether dye 화합물과 알칼리 금속(Na, K, Cs)과의 착물 스펙트럼에서 ${\lambda}_{max}$는 390~400nm의 띠 이동과 세기가 증가함을 보였다. 또한 추출상수값(Kex)은 음이온을 고정한 뒤 추출상수의 크기는 Crown ether dye-Ⅰ에서는$K^+$ < $Cs^+$ < $Na^+$의 순위를 얻었으며 crown ether dye-Ⅱ에서는 $Cs^+$ < $Na^+$ < $K^+$의 순서를 얻었다. 이러한 결과는 알칼리 금속의 이온반지름과 crown ether dye의 동공의 크기 관계와 알칼리 금속 이온의 전하밀도로 설명될 수 있고 도한 음이온의 변화에 따른 추출 상수의 크기는 두가지 crown ether dye에서 똑같이 $Cl^-$ < $Br^-$ < $I^-$ < picrate의 순위를 얻었다. 이는 음이온의 용매화효과 순서와 일치함을 보여주고 있다. 그리고 각각 합성된 crown ether dye화합물의 추출계수 비를 구하여 비교 고찰하였고, 알칼리 금속 이온들의 회수율은 약 90%의 양호한 실험값을 얻었다.

  • PDF