• 제목/요약/키워드: Metal coordination

검색결과 176건 처리시간 0.038초

Ambidentate Ligand의 금속 착물 (제1보). Isonitrosobenzoylacetone Imine 유도체와 니켈(Ⅱ)의 착물 (Metal Complexes of Ambidentate Ligands (I). Nickel(II) Complexes of Isonitrosobenzoylacetone Imine Derivatives)

  • 이만호;오대섭;이광우
    • 대한화학회지
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    • 제22권1호
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    • pp.19-24
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    • 1978
  • Ambidentate 리간드인 isonitrosobenzoylacetone imine 및 그 N-알킬치환체들의 새로운 니켈(II)착물 Ni(IBA-NH)(IBA-NR)를 합성하였다. 여기서 IBA-NH 및 IBA-NR (R=H, methyl, ethyl, n-propyl, iso-propyl, n-butyl 또는 benzyl)은 각각 isonitrosobenzoylacetone imine 및 그 N-알킬치환체를 표시한다. 합성한 니켈(II)착물들의 적외선, 핵자기공명, 전자스펙트라 및 자기모멘트등을 측정한 결과 이들 착물에서 IBA-NH 리간드는 이소니트로소기의 산소를 통하여 니켈에 배위되어 6각형 고리를 이루고 있으며, 그리고 IBA-NR 리간드는 이소니트로소기의 질소를 통하여 니켈에 배위되어 5각형 고리를 이루고 있음을 확인하였다. 이들 리간드의 배위 구조는 Bose 등에 의해 알려진 isonitrosoacetylacetone imine 및 N-알킬유도체들의 구조와 유사하다.

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N-메틸루티돈의 루미네센스에 관한 연구 (Luminescence Studies of N-Methyllutidone, an Unusually High Triplet Energy Sensitizer)

  • 심상철;현명호;채규호
    • 대한화학회지
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    • 제22권1호
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    • pp.45-51
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    • 1978
  • $77^{\circ}C$K 에탄올 매트릭스에서 N-메틸루티돈의 발광에 대한 연구를 하였다. 형광은 관찰되지 않았으나 양자 수득률이 0.1과 수명 0.2초의 강한 인광이 관찰되었다. 인광의 0-0 띠로부터 이 화물합의 삼중상태 에너지가 85.1kcal/mole임을 알았으며 2-헥센, 트란스-1,4-디클로로부텐-2와 같은 높은 삼중상태 에너지를 가진 올레핀들이 N-메틸루티돈에 의해 효과적으로 시스${\leftrightarrow}$트란스광이성질화 반응을 일으키는 것으로 보아 이 높은 삼중상태 에너지가 정당함을 알 수 있다. 0-0띠의 polarization이 음의 값을 갖는 것으로 부터 발광상태가 $({\pi},{\pi})^3$ 상태임을 알 수 있다. LiCl과 같은 알카리염의 양이온과 N-메틸루티돈이 배위결합을 함으로써 $({\pi},{\pi})^3$$(n,{\pi})^3$상태 사이의 에너지 차이가 크게 되기 때문에 알카리 금속염은 인광의 세기를 증가시킨다.

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Ambidentate 리간드의 금속착물 (제 3보). Isonitrosobenzoylacetone Imine 유도체와 팔라듐(Ⅱ)의 착물 (Metal Complexes of Ambidentate Ligands (Ⅲ). Palladium (Ⅱ) Complexes of Isonitrosobenzoylacetone Imine Derivatives)

  • 오대섭;이만호;김수한;박정학;이해운
    • 대한화학회지
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    • 제26권1호
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    • pp.31-35
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    • 1982
  • Amberdentate 리간드인 isonitrosobenzoylacetone imine 및 N-알킬 치환제들의 새로운 팔라듐(Ⅱ) 착물 Pd(IBA-NH)(IBA-NH') 및 Pd(IBA-NR)2를 합성하였다. 여기서 IBA-NH 및 IBA-NR (R: methyl, ethyl, n-propyl, n-butyl, benzyl)은 각각 isonitrosobenzoylacetone imine 및 그 N-알킬 치환제를 표시한다. 합성한 팔라듐(II) 착물들의 적외선, 핵자기 공명, 전자 스펙트라 등을 측정한 결과 이들 착물 중에서 Pd(IBA-NH)(IBA-NH')는 IBA-NH는 이소니트로소기의 산소를 통하여 팔라듐에 배위되어 6각형 고리를 이루며 IBA-NH'는 이소니트로소기의 질소를 통하여 배위되어 5각형 고리를 이루고 있음을 확인하였다. 그리고 Pd$(IBA-NR)_2$는 양쪽의 IBA-NR이 같이 이소니트로소기의 질소를 통하여 배위되어 5각형 고리를 이루고 있음을 확인하였다. 이들 리간드의 배위구조는 $Bose^5$등에 의하여 알려진 isonitrosoacetylacetone imine 및 그 N-알킬 유도체들의 구조와 유사하다.

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전이금속 촉매작용의 산화반응과 리간드 효과 (Transition Metal Catalysed Oxidation Reactions and Ligand Effects in Aprotic Solvents)

  • 김상복
    • 대한화학회지
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    • 제47권6호
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    • pp.585-590
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    • 2003
  • 코발트 산소 운반체인 N,N''-ethylenebis(3-methoxysalycylideneiminato)cobalt(II), Co(3MeOsalen)을 $25{\circ}C$에서 합성하였다. 이 착물과 하이드라조벤젠의 자외선 및 가시부분 광스펙트럼은 파장 범위 200-600 nm에서 비수용매 메탄올을 사용하여 연구하였다. 하이드라조벤젠의 산소와의 산화반응은 메탄올에서 Co(3MeOsalen) 촉매로 사용하였다. 트라이페닐포스핀($PPh_3$) 존재하에서, 반응속도는 감소하였으며 이는 촉매가 리간드 트라이페닐포스핀과 배위화합된 것으로 추정되며 촉매가 비활성인 Co(3MeOsalen)$(PPh_3)_2$으로 되어 속도가 급격히 떨어지는 것으로 생각된다. 리간드 트라이페닐포스핀과 하이드라조벤젠의 초기산화속도는 이론속도식, Rate=$k_1+k_2K_1[P]/1+K_1[P]+K_1K_2[P]^2$으로 측정되었다. 이것은 리간드가 메탄올 분자보다 더 좋지않은 σ-주게일 것으로 간주된다.

Amorphous Vanadium Titanates as a Negative Electrode for Lithium-ion Batteries

  • Lee, Jeong Beom;Chae, Oh. B.;Chae, Seulki;Ryu, Ji Heon;Oh, Seung M.
    • Journal of Electrochemical Science and Technology
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    • 제7권4호
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    • pp.306-315
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    • 2016
  • Amorphous vanadium titanates (aVTOs) are examined for use as a negative electrode in lithium-ion batteries. These amorphous mixed oxides are synthesized in nanosized particles (<100 nm) and flocculated to form secondary particles. The $V^{5+}$ ions in aVTO are found to occupy tetrahedral sites, whereas the $Ti^{4+}$ ions show fivefold coordination. Both are uniformly dispersed at the atomic scale in the amorphous oxide matrix, which has abundant structural defects. The first reversible capacity of an aVTO electrode ($295mAhg^{-1}$) is larger than that observed for a physically mixed electrode (1:2 $aV_2O_5$ | $aTiO_2$, $245mAhg^{-1}$). The discrepancy seems to be due to the unique four-coordinated $V^{5+}$ ions in aVTO, which either are more electron-accepting or generate more structural defects that serve as $Li^+$ storage sites. Coin-type Li/aVTO cells show a large irreversible capacity in the first cycle. When they are prepared under nitrogen (aVTO-N), the population of surface hydroxyl groups is greatly reduced. These groups irreversibly produce highly resistive inorganic compounds (LiOH and $Li_2O$), leading to increased irreversible capacity and electrode resistance. As a result, the material prepared under nitrogen shows higher Coulombic efficiency and rate capability.

Application of Bond Valence Method to Estimate the Valence Charge Distributi on in the Metal-to-Oxygen Bonding Spheres in Perovskites

  • Nhat, Hoang Nam;Chau, Dinh Van;Thuong, Dinh Van;Hang, Nguyen Thi
    • International Journal of Internet, Broadcasting and Communication
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    • 제7권1호
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    • pp.75-92
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    • 2015
  • This paper presents the application of the bond valence method to estimate the valence charge distribution in several perovskite systems: $La_{{\tilde{1}}x}Pb_xMnO_3$ (x=0.1-0.5), $La_{0.6}Sr_{0.{\tilde{4}}x}Ti_xMnO_3$ (x=0.0-0.25) and $La_{{\tilde{1}}x}Sr_xCoO_3$ (x=0.1-0.5); the reviewing of their crystal structures is also incorporated. The results showed the failure of the elastic bonding mechanism in all studied systems and revealed the general deficit of the valence charge in their unit cells. This valence deficit was not associated with the structural defects and was not equally localized in all coordination spheres. As the content of substitution increased, the charge deficit declined systematically from balanced level, signifying the transfer of valence charge from the ${\tilde{B}}O_6$ to ${\tilde{A}}O_{12}$ spheres. This transfer depended on the valence deviation of spheres and the average reached near 2 electron per unit cell. The possible impact of the limitted accuracy of the available structural data on the bond valence results has also been considered.

Synthesis of the Water Dispersible L-Valine Capped ZnS:Mn Nanocrystal and the Crystal Structure of the Precursor Complex: [Zn(Val)2(H2O)]

  • Hwang, Cheong-Soo;Lee, Na-Rae;Kim, Young-Ah;Park, Youn-Bong
    • Bulletin of the Korean Chemical Society
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    • 제27권11호
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    • pp.1809-1814
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    • 2006
  • The L-Valinate anion coordinating zinc complex, [$Zn(val)_2(H-2O)$], was isolated and structurally characterized by single crystal X-ray crystallography. The crystal possess orthorhombic symmetry with a space group $P2_12_12_1$, Z = 4, and a = 7.4279(2)$\AA$, b = 9.4342(2)$\AA$, c =20.5862(7)$\AA$ respectively. The compound features a penta-coordinate zinc ion in which the two valine anion molecules are directly coordinating the central zinc metal ion via their N (amine) and O (carboxylate) atoms, and an additional coordination to zinc is made by water molecule (solvent) to form a distorted square pyramidal structure. In addition, further synthesis of the valine capped ZnS:Mn nanocrystal from the reaction of [$Zn(val)_2(H-2O)$] precursor with $Na_2S$ and 1.95 weight % of $Mn^{2+}$ dopant is described. Obtained valine capped nanocrystal was water dispersible and was optically characterized by UV-vis and solution PL spectroscopy. The solution PL spectrum for the valine capped ZnS:Mn nanocrystal showed an excitation peak at 280 nm and a very narrow emission peak at 558 nm respectively. The measured and calculated PL efficiency of the nanocrystal in water was 15.8%. The obtained powders were characterized by XRD, HR-TEM, and EDXS analyses. The particle size of the nanocrystal was also measured via a TEM image. The measured average particle size was 3.3 nm.

Synthesis, Characterization, and Crystal Structures of Iron(Ⅱ) and Manganese(II) Complexes with 4,7-bis(2-pyridylmethyl)-1-thia-4,7-diazacyclononane

  • Delong Zhang;Daryle H. Busch;Nathaniel W. Alcock
    • Bulletin of the Korean Chemical Society
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    • 제19권9호
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    • pp.897-906
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    • 1998
  • A new synthesis has been developed for 1-thia-4,7-diazacyclononane and the complexation behavior of a particular derivative has been explored. The pentadentate ligand 4,7-bis(2-pyridylmethyl)-l-thia-4,7-diazacyclononane ([9]$N_2SPY_2$) and its iron(Ⅱ) and manganese(Ⅱ) complexes were prepared and characterized. Magnetic moments of 5.17 and 5.90 μB respectively, indicate that the iron(Ⅱ) and manganese(Ⅱ) complexes are high spin. Charge transfer transitions (d-π*) occur for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$at 27027, 25000, and 24390 cm-1 for X=$H_2O$, Cl-, and OH-, respectively. In acetonitrile solution, the cyclic voltammogram of the manganese(Ⅱ) complex exhibits a redox couple at 0.92 V vs. NHE while the redox potentials for [Fe(Il)([9]$N_2SPY_2)(X)]^{n+}$ are 0.70, 0.66, and 0.37 V vs. NHE for X=$H_2O$, Cl-, and OH-, respectively. The d-π* charge transfer energy and Fe(Ⅱ)/Fe(Ⅲ) redox potential for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$ increase in the same order: $H_2O>Cl^- >OH^-$. The crystal structures of the iron(Ⅱ) and manganese(Ⅱ) complexes reveal that the metal ions are sixcoordinate, binding to four nitrogen atoms and a sulfur atom from the pentadentate ligand, as well as a chloride anion, with the chloride and sulfur atoms in cis positions. The two metals have similar coordination geometries, which are closer to trigonal prismatic than octahedral. In both iron and manganese complexes, the M-N($sp_3$) trans to Cl- is 0.07 Å longer than the one cis to Cl- , and M-N($sp^2$) trans to S is 0.05 longer than the one cis to S atom.

남동해 연안 퇴적물 내 미량금속 분포 및 생태위해도 평가 (Trace Metal Distribution and Ecological Risk Assessment in Marine Sediments from the Southeast Coastal Areas of Korea)

  • 황동운;최민규;임재현;이인석;이가람;나수진
    • 한국수산과학회지
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    • 제56권4호
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    • pp.438-448
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    • 2023
  • The concentrations of trace metals and organic matters in marine sediments collected from southeast Korean coastal areas were investigated. The primary purpose of this study was to evaluate the contamination status, spatial distribution and potential ecological risks associated with the physiochemical composition in the studied areas. We found that the concentrations of trace metals in marine sediments were as follows: Fe > Mn > Zn > Cr > Pb > Cu > As > Cd > Hg. According to the sediment quality guidelines (SQGs) of Korea, concentrations of Zn, Cr, Cu and Cd at all sampling sites were below threshold effect levels (TEL). However, concentrations of As, Hg, and Pb (i.e., at the 94-98% of sampling sites), were below the TEL. In addition, concentration factors (CF) in the surveyed area were found to be associated with low ecological risks, whereas As, Hg, and Cu showed moderate to high risk levels in some inner parts of the studied bays. Finally, the pollution load index (PLI) and ecological risk index (ERI) of the elucidated metals were linked to moderate ecological risk, pointing to the possibility of being deleterious to some benthic organisms.

디메틸아크릴아마이드 변성 폴리오가노실록산을 이용한 액상 실리콘 고무의 제조와 그 특성 (Preparation and Characteristics of Liquid Silicone Rubber Using Polyorganosiloxane Modified with Dimethylacrylamide)

  • 강두환;이병철
    • 폴리머
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    • 제28권2호
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    • pp.143-148
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    • 2004
  • 옥타메틸싸이클로테트라실록산과 1,3,5-트리메틸싸이클로트리실록산 및 1,3,5,7-테트라비닐-1,3,5,7-테트라메틸싸이클로테트라실록산을 테트라메틸암모늄 실록산올레이트 촉매 하에서 1,1,3,3-테트라메틸디실록산과 평형중합으로 이들을 공중합시켜 $\alpha$,$\omega$-하이드로겐 폴리(메틸-디메틸-메틸비닐)실록산 전구체를 제조하였다. 제조된 $\alpha$,$\omega$-하이드로겐 폴리(메틸-디메틸-메틸비닐)실록산 전구체에 디메틸아크릴아마이드를 백금촉매 작용 하에서 반응시켜 아크릴아마이드 변성 $\alpha$,$\omega$-하이드로겐 폴리(메틸-디메틸-메틸비닐)실록산 전구체 (APMDMS)를 제조하였으며 여기에 금속산화물인 NiO, FeO를 배위결합시켜 금속산화물이 2차 결합으로 부가된 APMDMS-MO를 제조하였다. 제조된 화합물의 구조를 FT-IR과 $^1$H-NMR로 분석하여 확인하였다. $\alpha$,$\omega$-비닐 폴리디메틸실록산과 APMDMS-MO를 백금촉매 존재 하에서 컴파운딩시켜 금속산화물 함유 액상 실리콘 고무 복합체를 제조하였으며 이 화합물을 이용하여 제조된 쉬이트의 열 전도도는 0.29 W/mW로 액상 실리콘 고무 복합체의 0.215 W/mK 보다 우수하였고 체적 저항은 1.64${\times}$$10^{5}$$\Omega$ㆍcm로 낮은 값을 나타내었다. 또한 디메틸아크릴아마이드 변성 액상 실리콘 고무 복합체의 기계적 및 열적특성은 UTM과 TGA로 측정하였다.다.