수용성 비이온고분자인 Polyvinylalcohol (PVA), Polyvinylpyrrolidone (PVP), Hydroxypropyl cellusoe (HPC)와 iodine과의 착물 형성에 대한 계면활성제의 영향을 알아보기 위해 Sodiumdodecylsulfate을 포함하는 수용액에서 이들 사이의 반응을 수행하였다. PVP와 HPC에서 tri-iodide band의 적색 이동에 의하여 착물이 만들어졌다는 것을 알게되었고, PVA-iodine 착물에서는 500 nm 부근에서 고유의 특색있는 띠를 나타내었다. SDS 계면활성제의 존재는 PVA-iodine 착물의 파괴를 가져왔고, 고유의 푸른색도 사라지게 만들었다. 그러나 SDS 단량체는 PVP, HPC와 iodine의 착물 형성을 도와주는 경향을 나타내었다. 고분자 용액에서 겔이 만들어지는 것을 방해하는 n-propanol은 고 분자-iodine 착물이 형성되는 것을 도와주었다. SDS가 있을 때와 없을 경우의 영향을 알아보기 위해 순 수한 HPC와 HPC-iodine 착물을 만들고 이들의 성질을 조사하였다.
정삼투 분리막 용도에 적합한 폴리아미드 복합막의 제조에 있어 지지층의 극성 및 공극률이 폴리아미드 구조 및 정삼투 분리막 투과 성능에 미치는 영향을 살펴보기 위하여 클레쏘킬레이트 금속착물(0.1-0.5중량%)이 함유된 폴리술폰(18중 량%) 용액을 상전이 공정을 통하여 지지층을 제조하였다. 제조된 지지층 상에 방향족 폴리아미드 활성층을 제막하였다. 다공 성 PSF 지지층 제조를 위하여 상대적으로 낮은 폴리술폰(12중량%) 용액을 이용한 지지층을 폴리에스터 필름상에서 제조한 후 필름을 제거하고 제조된 지지층 상에 방향족 폴리아미드 활성층을 제막하였다. 제막된 시편 중 폴리술폰(18중량%)/금속착 물(0.5중량%)로 만들어진 FO막은 유량 9.99 LMH, reverse salt flux 0.77 GMH로 HTI의 상용막(10.97 LMH, 2.2 GMH)과 비교해도 거의 비슷한 유량값과 향상된 RSF 값을 얻을 수 있었다. 캐스팅 용액의 금속착물의 첨가로 활성층 두께가 줄어들 었으나 제거효율은 향상되는 결과를 얻을 수 있었다.
단일막이 가지는 저유량 한계성과 복합막이 가지는 용질 역확산 현상을 완화하기 위한 방법으로 지지층 내 금속 착물이 균일하게 정착된 PSF 고분자 지지층을 제조하였다. 부직포의 두께와 밀도를 조절하였으며 지지층 제조법 최적화 이후 Fe(II)-chelate 착물을 포함하는 정삼투 분리막을 제조하였다. 지지층 제조방법에 있어 고분자의 부직포 함침 속도 조절이 정삼투 분리막 지지층의 구조결정에 가장 중요한 역할을 함을 볼 수 있었다. 고분자의 상 전이 과정에 있어서 금속 착물과 같은 극성물질의 존재가 용매 -비용매 치환 속도에 영향을 주어 지지층 구조 조절을 유도하였으며 그 결과, 용질 역확산이 약 0.07 - 0.11 GMH의 값을 가지는 높은 제거효율의 FO막을 제조할 수 있었다.
본 연구는 거대고리 금속 이온 착화합물과 유도체를 이용하여 미세 다공성 구조를 가지는 분리막의 제조에 관한 것이다. 고분자와 금속이온 리간드 착물 시스템을 이용함으로써 기존의 방법들에 비해 상 전이 과정을 보다 정교하게 제어할 수 있었다. 금속염, cyclohexanedione dioxime, hydroxyphenylboronic acid와의 축합 반응을 통하여 금속 clathrochelate 착물을 얻을 수 있었다. PES, PVP, BE와 금속 clathrochelate 착물을 DMF에 녹인 후 비용매 유도 상 전이법을 통하여 유무기 혼성 고분자막을 제조하였다. 제조된 분리막의 구조는 FE-SEM과 microflow permporometer로 조사하였다. p-Hydroxyphenyl group 을 가지는 Fe(II) clathrochelate 착물의 첨가는 분리막의 구조에 있어 기공 크기 분산도를 좁혀주고, 표면의 기공 밀도를 높여 주었으며 최대 기공 크기를 감소시킴을 볼 수 있었다.
Kinetic studies on the ligand substitution reactions of cyanocomplexes were performed in several micellar solutions. It showed the observed rate constants was found to be independent of the entering ligand concentration at high concentration of cyanopyridine and pyrazinecarboxylate. We could see also that in nonionic and anionic micellar solutions no influence of changes in the surfactant concentration on the observed rate constants was found. Taking into account the hydrophilic nature of the cobalt complex, the cobalt complex molecule was expected to be located in the aqueous phase of the micellar systems, where the reaction would take place. In cationic micellar solutions, a small increase in the observed rate constant was found when the cationic surfactant concentration increased. After reaching a maximum, the rate constant decreased on increasing surfactant concentration and subsequently it reached a plateau, where the observed rate constant was independent of changes in the surfactant concentration.
Among the efforts to increase the efficiency of organic light-emitting device (OLED), there is a way: doping phosphorescent materials. As a phosphorescent material, complexes of heavy transition metal, platinum, were synthesized. Cl- ion and phenyl group were used as ancillary ligands with 2-(2-pyridyl)benzimidazole (pbi) as a chromophore. The complexes were analysed by FAB-mass spectrometer and absorption and emission spectra were obtained. A phenyl group was able to shift the emission band of the complex even if it's not a chromorphore.
The structure of a carbon monoxide sorption complex of dehydrated fully Ca2+-exchanged zeolite X, |Ca46(CO)27|[Si100Al92O384]-FAU, has been determined in the cubic space group Fd 3 at 21℃ (a = 24.970(4) ) by single-crystal X-ray diffraction techniques. The crystal was prepared by ion exchange in a flowing stream of 0.05 M aqueous Ca(NO3)2 for three days, followed by dehydration at 400℃ and 2×10-6 Torr for two days, and exposure to 100 Torr of zeolitically dry carbon monoxide gas at 21℃. The structure was determined in this atmosphere and was refined, using the 356 reflections for which Fo 〉 4Σ(Fo), to the final error indices R1 = 0.059 and wR2 = 0.087. In this structure, Ca2+ ions occupy three crystallographic sites. Sixteen Ca2+ ions fill the octahedral site I at the centers of hexagonal prisms (Ca-O = 2.415(7) a). The remaining 30 Ca2+ ions are found at two nonequivalent sites II (in the supercages) with occupancies of 3 and 27 ions. Each of these Ca2+ ions coordinates to three framework oxygens, either at 2.276(10) or 2.298(8) a, respectively. Twenty-seven carbon monoxide molecules have been sorbed per unit cell, three per supercage. Each coordinates to one of the latter 16 site-II Ca2+ ions: C-Ca = 2.72(8) a. The imprecisely determined N-C bond length, 1.26(14) a, differs insignificantly from that in carbon monoxide(g), 1.13 a.
Diphosphine dinuclear gold(I) complexes were synthesized from the reaction of bridged diphosphines and gold ions. As a bridged diphosphine, 1,2-bis(diphenylphosphino)metbane (dppm) or 1,1'-Bis(diphenylphosphino) ferrocene (dppf) was introduced. As anionic ligands, CI was first coordinated to Au, resulting in (diphosphine)(AuCl)2. Then, the ligand, SPh, was substituted for Cl in the chloride complex to give (diphosphine)(AuSPh)2. As a result, three digold complexes, (dppm)(AuCl)2. (I), (dppf)(AuCl)2. (II), and (dppf)(AuSPh2. (III) were prepared in this study. The thermal properties were investigated at first hand to confirm that the gold complexes were in fact formed. The digold complexes were decomposed above 200℃ while the ligand, dppm or dppf, melts under 180℃ The photoluminescence (PL) spectra of the spin-coated thin films showed the maximum peak at 590, 595, and 540nm for the complex, I, II, and III, respectively. These complexes were found to give the orange color phosphorescence. Therefore, these digold complexes can be candidates for orange-red phosphorescent materials in organic electroluminescent devices (OELD). Further studies on application of the complexes as a dopant in an emitting layer are in progress in our laboratory.
Recently, the phosphorescent organic light-emitting devices (OLEDs) have been extensively studied for their high internal quantum efficiency. In this study, we synthesised several phosphorescent metal complexes, and certified their composition using NMR. We also investigated the characteristics of the phosphorescent OLEDs with the green emitting phosphor, Ir(ppy)3. The devices with a structure of indium-tin-oxide(ITO)/N,N'-diphenyl-N,N'-(3-methylphenyI-1,1'-biphenyl-4,4'-diamine (TPD)/metal complex doped in host materials/2,9-dimethyl-4,7-diphenyl-l,10-phenanthroline(BCP)/tris (8-hydroxyquinolinato) Aluminum(Alq3)/Li:Al/Al was fabricated, and its electrical and optical characteristics were studied. By changing the doping concentration of tris(2-phenylpyridine)iridium (Ir(ppy)3), we fabricated several devices and investigated their characteristics.
The Mo(V) di-μ-oxo type [Mo2O4(H2O)2L2] SO4 complexes(L: 2,2'-dipyridyl,4,4'-ethylenedianlline) have been prepared by the reaction of [Mo2O4(H2O)6]SO4 with a series of chelate ligands. These complexes are completed by two terminal oxygens arranged trans to one another and each ligand forms a chelate types. In Mo2O4(H2O)2L2, two H2O coordinated at trans site of terminal oxygens. The prepared complexes have been characterized by elemental analysis, infrared spectra, 1H nuclear magnetic resonance spectra, and thermal analysis(TG-DTA). In the potential range -0.00V to -1.00V at a scan rate of 50mVs-1, a cathodic peak at -0.81V ~ -0.87V (vs SCE) and an anodic peak at -0.61V ~ -0.63V (vs SCE) have been observed in aquous solution. We infer these redox are irreversible reaction.
Eu(III) exhibits one electron-transfer reduction at E1/2 = -0.564 V(vs. Ag/AgCl) and the hypersensitive peak at 615 ㎚ corresponding to 5D0→7F2 transition in 0.1 M LiClO4 aqueous solution. Upon the addition of 2,6-pyridine dicarboxylic acid(PDA) to the Eu(III) aqueous soultion, the reduction potential shifts negatively and the PDA, and the Eu(III)-PDA complex emits great fluorescence than free-Eu(III) ion at 615 nm. The results are interpreted in term of the electrochemical and spectrofluorometric studies.
Langmuir-Blodgett(LB) 법은 미래의 분자전자소자를 위한 가장 유력한 수단이며, 이러한 분자박막 소자는 그 성질이 분자는 배향에 영향을 박데 되므로 현재 새로운 물질을 이용하여 분자전자소자의 제작에 있어 관심을 모으고 있다. 본 연구에서는 (N-docosyl quinolinium)-TCNQ(1:2) 전하 이동 착물 LB 막의 분자 배향을 UV/vis 편광흡수 스펙트럼과 FT-IR transmission 및 reflection-absorption 스펙트럼의 흡수강도를 비교하여 정량적으로 평가하였다. 그 결과 TCNQ의 transition dipole moment의 각은 약 56~58。 였으며, 알킬 고리의 경사각은 약 11.1~13。였다. 제작된 Z-형 LB 막의 표면은 고압에서 중앙 높이 차가 3~4Å으로 평탄하였다.
In this study, ultra-thin films of (N-docosyl quinolinium)-TCNQ(1:2) complex were prepared on the hydrophilic substrate by Langmuir-Blodgett(LB) technique. The characteristics of π-A isotherms were studied to find optimum conditions of deposition by varying temperature of subphase, compression speed of barrier and amount of spreading solution. Using UV-vis spectra, capacitance and thickness, deposition of LB films was confirmed together with the thickness of the naturally oxidized aluminum film inside a device and dielectric constant of (N-docosyl quinolinium)-TCNQ(1:2) complex. The dielectric constant of LB film was about 4.59~5.58. The electrical properties of (N-docosyl quinolinium)-TCNQ(1:2) complex were investigated at room temperature. The conductivity of this film measured by the direction of either vertical or horizontal axis was found to have a quite different value.
UO2분말에 PVA-Al(III) 착물과 AlOOH를 각각 0.03~1.0wt%를 첨가하여 소결체를 제조한 후 소결체 특성을 비교하였다. PVA-Al(III) 착물과 AlOOH는 1000˚C의 소소분위기에서 열분해하는 경우 생성상은 θ-Al2O3이었다. 순수 UO2분말에 비해 AlOOH가 첨가된 혼합 분말의 곁보기 밀도는 더 높았고, PVA-Al(III) 착물이 첨가된 혼합 분말은 더 낮은 겉보기 밀도를 보였다. AlOOH가 첨가된 소결체의 경우 약 800˚C 부근에서 치밀화가 시작되었지만, PVA-Al(III) 착물이 첨가된 소결체의 경우에는 약 900˚C에서 치밀화가 시작되었다. 기공 크기 분포는 AlOOH가 첨가된 UO2소결체의 경우에 monomodal 형태로, 그리고 PVA-Al(III) 착물의 첨가된 소결체의 경우에는 bimodal 형태로 나타났다. 결정립 크기는 1wt% 첨가시 AlOOH가 첨가된 UO2소결체의 경우에 약 13μm이었지만, PVA-Al(III) 착물의 첨가된 소결체의 경우에는 약 36mum까지 성장하는 현저한 효과를 확인하였다.
본 연구에서는 (N-docosyl quinolinium)-TCNQ (1:2) 착물의 LB초박막을 제작하였다. LB막의 누적을 위한 최적조건을 구하기 위하여 subphase 온도, barrier 압축속도 및 분산량을 변화시키면서 표면압-면적(π-A) 등온선 특성을 측정하였다. 그리고 전이비, UV-vis의 최대 흡광도, 정전용량 및 두께를 측정하여 LB막의 누적상태를 확인하였다. 그 결과 분자수준으로 잘 제어된 양호한 LB막이 제작되었음을 알 수 있었다..
The Mo(V) di-μ-oxo type [Mo2O4(H2O)2L]Cl2 complexes(L: 4,4'-Diphenyl-2,2'-dipyridyl, 4,4'-Dimethyl-2,2'-dipyridyl, 4,7-Diphenyl-1,10-phenanthroline) have been prepared by the reaction of [Mo2O4(H2O)6]2+ with a series of chelate ligands. These complexes are completed by two terminal oxygens arranged trans to one another and each ligand forms a chelate types. In Mo2O4(H2O)2L two H2O coordinated at trans site of terminal oxgens. The prepared complexes have been characterized by elemental analysis, infrared spectra, electronic spectra, 1H nuclear magnetic resonance spectra, and thermal analysis(TG-DTA). In the potential range -0.00V to -1.00V at scan rate of 50mVs-1, a cathodic peak at -0.83V ~ -0.88V (vs SCE) and an anodic peak at -0.54V ~ -0.88V (vs SCE) have been observed in aquous solution. The ratio of the cathodic to anodic current(Ipc/Ipa) is almost 2, we infer that redox is irreversible as dimer forms broken.
Tris(8-hydroxyquinoline)-aluminum complex(AlQ3) having greenish luminescent characteristics was synthesized and it was confirmed with UV-Vis absorption spectroscopy, elemental analysis, and FT-IR spectroscopy that AlQ3 was successfully synthesized. Thin films of AlQ3 having multilayer structure were prepared by spin coating method and vacuum evaporation technique. Photopluminescent characteristics of these films were investigated by Luminescence spectroscopy and Current-Voltage(I-V) characteristics of these films were also investigated.
In this research, ultra-thin films of organic charge transfer complex were deposited on to ordinary microscope slide-glass subtrates with a Langmuir-Blodgett technique. π-A isotherm characteristics of these complex were studied in order to find optimum conditions of deposition by varying temperature of subphase, compression speed, and spreading amount. Transfer ratio of these films were studied during the process of deposition. The UV-visible absorbance spectra of LB films were measured to find state of deposition by varing layer number. The observed optimum conditions of surface, pressure, spreading amount, and dipping speed for depositing LB films(Y-type) were 38m/Nm, 150μl and 5mm/min, respectively. Since the tansfer ratio is close to 100%, the monolayer on the subphase seems to be well transferred to the solid substrate. The thickness of the film was well-controlled as the UV-vis absorbance of films were changed linear according to the number of layers.
Hexyltriphenylphosphonium-TCNQ(HTPP-TCNQ) complex for preparing organic thin film by Langmuir-Blodgett technique was synthesized from LiTCNQ and Hexyltriphenylphosphonium bromide. The structure of the new complex was confirmed by 1H NMR, 31P NMR, IR, UV spectroscopies, TGA and elemental analysis. A stability to spreading solvent, which is acetonitrile, ethylacetate, ethanol and acetonitrile-ethylacetate(1:1 v/v), of HTPP-TCNQ complex was investigated by UV-visible spectrophotometer. The complex was stabilized in acetonitrile, ethylacetate, aceton, acetonitrile-ethylacetate (1:1 v/v) for 6 h.
A stability to the spreading solvent, which is acetonitrile, benzene, chloroform and acetonitrile-benzene(1:1, v/v) of (3-Alkyl benzimidazdium)-TCNQ(1:2) complex was investigated by UV-visible spectrometer and was confirmed stabilized on acetonitrile, acetonitrile-benzene (1:1, v/v) for five hours. Using Ultra pure water as subphase for Langmuir-Blodgett(LB) films, it was achived successively to fabricate the Y-type LB films of (3-Alkyl benzimidazolium)-TCNQ(1:2) complex. For the identification of (3-Alkyl benzimidazolium)-TCNQ(1:2) complex, UV-visible spectra was recorded on HP 8452A spectrometer.