TTF(COO^-)_4 음이온이 삽입된 층상형 이중수산화물(LDH)

노동윤,서은미,한상미 서울여자대학교 자연과학연구소 1997 자연과학연구논문집 Vol.9 No.-

본 연구에서 마그네슘과 알루미늄 LDH에 C_3S_3(COO^-)_2와 TFF(COO^-)_4를 음이온 교환은 통한 삽입(intercalation)하여 합성하고 적외선 분광과 x-선 회절 분석법에 의해 분석하였다. C_3S_3(COO^-)_2의 경우 적외선 분석에 의해서는 카르복실기의 존재가 확인되었지만 x-선 회절 분석에 의하면 층 자체가 깨어짐을 볼 수 있다. Mg^2+/Al^3+/NO_3^-에서 한 층의 간격이 7.7Å 인데 비해 Mg^2+/Al^3+/TTF(COO^-)_4의 한 층의 간격이 7.87Å로 음이온 교환에 의해 층 간격이 넓어졌음을 알 수 있다. 그러나 이 층의 간격이 TTF(COO^-)_4가 층에 수직인 상태로 삽입될 정도로 넓지 않아 층에 평행인 상태로 들어가 있음을 알 수 있다. 만약 M^2+/M^3+의 비를 조절하여 합성한다면 TTF(COO^-)_4가 수직인 상태로 삽입될 수 있음을 예측할 수 있다. New layered double hydroxide(LDH) intercalation complex of the type [Mg_l-xAl_x(OH)_2s][TTF(COO-)_4]_x/4g·zH_2O has been prepared by the direct method. According to the XRD measurement, interlayer space of the TTF(COO-)_4-intercalated complex(7.84A˘ ) is larger than that of NO_3 (7.7A˘). From these data we propose that TTF(COO-)_4 anions be lying in LHD layer, which is identified from the calculation of the charge density.

자기조립 단분자막(SAM) 제작에 사용할 티올 유도체의 합성과 분석

노동윤 서울여자대학교 자연과학연구소 2001 자연과학연구논문집 Vol.13 No.-

Dodecanethiol derivative of 1,3-dithiole-2-thione (HSC12MT-DTT) has been synthesized to be used in the developement of functional self-assembled monolayer (SAM). This thiol compound is characterized by IR and 1H-/13C-NMR. Its electrochemical properly is also investigated by cyclic voltammetry.

새로운 이핵 다금속 화합물

노동윤,이하진,서은미 서울여자대학교 자연과학연구소 1999 자연과학연구논문집 Vol.11 No.-

백금과 철이 포함되는 새로운 이핵 다금속 화합물인 (dppf) Pt (deydt), (dppf) Pt (ebmdt)와 (dppf) Pt (bmddt)를 합성하여 IR, UV, 고분해능 FAB 질량분석, x-선 구조분석, 순환 전압-전류법으로 분석하였다. (dppf)Pt(ebmdt)와 (dppf)Pt(bmddt)의 순환 전압-전류법 분석결과 리간드의 가역적인 산화가 먼저 일어난 후 약 1.4 V에서 가역적인 〔(dppf)Pt〕^2+의 산화가 관측되었다. 그러나 (dppf)Pt(deydt) 화합물의 경우 1. 25 V에서 가역적인 〔(dppf)Pt〕^2+의 산화가 일어난 후 1. 45 V에서 리간드의 분해로 예상되는 비가역성 산화 피이크가 관찰되었다. (dppf)Pt(deydt) 화합물의 x-선 구조분석을 185 K의 저온에서 수행하였음에도 말단의 두 -COOCH_2CH_3 기 가운데 하나가 심하게 disorder되어 있는 것으로 분석되었다. New platinum(Ⅱ) complexes, (dppf)Pt(deydt), (dppf)Pt(ebmdt) and (dppf)Pt(bmddt)(dppf: 1,1'-bis(diphenylphosphino) ferrocene; deydt: diethylester ylidenedithiolate; ebindt: 1,2-ethylenebis(methylester)-1,2-dithiolate; bmddt:5,6-bis(methylester)-1,4-dithiin-2,3-dithiolate) were synthesized and analyzed by FT-IR, UV-vis, high-resolution FAB Mass, SEM and cyclic voltammetry. Single crystal of (dppf)Pt(deydt)·(CH_3OH) was grown in dichloromethane/methanol, the molecular structure of which was clucidated by x~ray structure analysis. Crystal data at 185±2 K are a=10.6290(4), b=23.3624(10), c=17.5956(7) Å, β=105.8930(10)°, P2(1)/c, V=4202.3(3) Å^3, Z=5, R=0.0819 and wR=0.1988. According to the cyclic voltammetry, ligand oxidation occurred at lower potential than that of [(dppf)Pt]^2 for (dppf)Pt(ebmdt) and (dppf)Pt(bmddt), however, [(dppf)Pt]^2 oxidation was followed by the ligand decomposition for (dppf)Pt(deydt) complex.

유기전자물질의 전구체인 (±)-4,5-phenylethylenedithio-1,3-dithiole-2-thione의 새로운 합성법과 그 이용

노동윤,이하진 서울여자대학교 자연과학연구소 1995 자연과학연구논문집 Vol.6 No.-

A precursor to organic electronic materials, (±)-4,5-phenylethylenedithio-1,3-dithiole-2-thione, was synthesized by the direct thermal reaction of loigomeric 1,3-dithiole-2,4,5-trithione, which was easily prepared by iodine oxidation of (TBA)_2[Zn(dmit)_2] in acetone, and styrene. This reaction is proceeded via [2+4] cycloaddition between oligomeric diene and styrene as a dienophile. Compared with the salt elimination method reported already, this new pathway saves more than one reaction step and deals with relatively inert material, 1,3-dithiole-2,4,5-trithione, to moisture and common organic solvents. It is also revealed that this compound can be used as a ligand of metal coordinated complex such as Ni(phdt)_2.

Electrochromic Properties of (P2)PtL Complexes (P2 = 3,4-Dimethyl-3’,4’-bis(diphenylphosphino)tetrathiafulvalene; L = 2Cl, C6H4S2, C3S5)

노동윤,신경순,Su-Kyung Lee 대한화학회 2009 Bulletin of the Korean Chemical Society Vol.30 No.12

로손시약과 1,8-디케톤 화합물의 이상 반응

노동윤,이하진,김영윤 서울여자대학교 자연과학연구소 1997 자연과학연구논문집 Vol.9 No.-

The new 1,3-dithiole-2-thione compound fused with diphenyl-containing ?? was synthesized by an unusual reaction of Lawesson's reagent ?? with 1,8-diketone and identified with FT-lR, El-MS and ^l3C-NMR. The reaction of Lawesson's reagent and diketone compounds gives different results depending on the property of functional group at a-position of ketone. This method can be developed as a new synthetic method of multisulfur compound which may be utilized as a precursor of organic conductors. Compound ?? will be a good candidate for the precursor of new TTF derivatives, too.

새로운 이핵 백금-디티올렌 화합물의 합성과 확인

노동윤,서은미,이명환 서울여자대학교 자연과학연구소 1997 자연과학연구논문집 Vol.8 No.-

중성 리간드인 dppf를 사용하여 새로운 백금 화합물을 합성하고 적외선과 자외선 분광법에 의해서 분석하였다. 적외선 분광법에 의해서 페닐기의 방향족 C=C의 신축진동이 1600cm-1~1400cm-1에서 확인되었으며, dmit 화합물에서는 1053.2cm-1에서 C=S 신축진동이, i-mnt 화합물에서는 2210.6cm-1에서 C=N 신축진동이 확인되었다. 자외선 분광법에 의해서는 400nm~500nm에서 매우 약한 페로센의 d-d 전자전이를 보였다. 또한 dmit 화합물에서 C=S의 전자전이가 466nm에서 관측되었다. New platinum(II) complexes containing 1.1'-bis(diphenylphosphino) ferrocene (dppf) as a neutral ligand and 1.2-dithiolenes (dmit : dimercapto isotrithione; dddt : 5.6-dihyro-1.4-dithiin-2.3-dithiolate; phdt : 5-phenyl-6-hydro-1.4-dithiin-2.3-dithiolate; dphdt :5.6-diphenyl-1.4-dithiin-2.3-dithiolate; mtdt : 1.2-bis(methylthio)ethylene-1.2-dithiolate) or 1.1-dihiolene (i-mnt : isomalononitriledithiolate) were synthesized in three-solvent system (benzene : methanol : water = 1 : 1 : 1). The single crystals were grown by diffusion method using dichloromethane and methanol in freezer. These compounds were characterized by FT-IR and UV-vis spectroscopic methods : In the FT-IR spectra, aromatic C=C stretching vibrations near 690~750cm-1 were observed in all Pt(dithiolene)(dppf) complexes. C=S stretching vibration of dmit ligand and C=N i-mnt ligand were also indexed at 1053.2cm-1 and 2210.6cm-1, respectively. electronic transition of phenyl group was observed between 215nm and 260nm while electronic absorption characteristic of C=S in dmit ligand appeared at 466nm in UV-vis spectra.

다황리간드를 갖는 새로운 니켈 착화합물의 합성과 전기 화학적 특성 연구 : (TPP) [Ni(dmbit)₂](TPP : tetraphenylphosphonium) (TPP) [Ni(dmbit)₂](TPP : tetraphenylphosphonium)

노동윤,강미정 서울여자대학교 자연과학연구소 1995 자연과학연구논문집 Vol.6 No.-

A new nickel complex with multisulfur ligand, (TPP) [Ni(dmbit)_2] where TPP is tetraphenylphosphonium and dmbit is dimercaptobenzene isotrithione, has been synthesized from (TPP) [Ni(dmbit)_2] by cation exchange reaction and successive oxidation step by both chemical and electrochemical methods. In the electrochemical method, microcrystals of monocationic complex were grown on the surface of platinum(+) electrode while polycrystals of dicationic one were on the (+) cell bottom. That is, two reaction processes(cation exchange by diffusion and electrochemical oxidation) were occurred simultaneously in one electrochemical cell. The cyclic voltamogram of dicationic TPP-complex shows two reversible curves at 36mV and 432mV upon reduction processes of [Ni (dmbit)_2]^2- → [Ni (dmbit)_2]^1- and [Ni (dmbit)_2]^1- → [Ni (dmbit)_2]^0, respectively. The potential difference (△E1/2=396mV) of this complex exceeds those of TBA-salts and Ni-dmit complexes, which means that TPP-salt might be inferior in electrical conductivity to TBA-salt as well as Ni-dmbit complex to Ni-dmit one in general.

Heteroleptic Binuclear Palladium(II) Complexes with P2Pd(S2) Cores: X-ray Crystal Structures of (PdCl2)2(μ-Ph2PC≡CPPh2)2 and [Pd(MET)]2(μ-Ph2PC≡CPPh2)2 where MET is (Z)-1,4-Dimethoxy-1,4-dioxobut-2-ene-2,3-dithiolate

노동윤,신경순 대한화학회 2008 Bulletin of the Korean Chemical Society Vol.29 No.12

소중합 디엔체인 1,3-dithiole-2,4,5-trithione의 Diels-Alder 형태의 [2+4] 고리화 첨가 반응에 관한 연구

노동윤,이하진,김영윤 서울여자대학교 자연과학연구소 1997 자연과학연구논문집 Vol.8 No.-

A Diels-Alder type [2+4] cycloaddition reaction of oligomeric diene (1,3-dithiole-2,4,5-trithione : (C3S5)n) with dienophiles containing warious functional groups was studied. Extended multisulfur system was achieved via [2+4] cycloaddition of TTF(1). Quinone(4), dienophiles containing cyanyl group(5-7), triple bond(14-17) and conjugated double bonds (25,26), however, failed to form cycloadducts with (C3S5)n. the reaction of (C3S5)n with dienophiles containing electron withdrawing groups such as -Co2CH3(18), phenyl(19-24), ferrocenyl(27,28), pyridyl(29,32) group was readily achieved. In case of asymmetrical dienophiles such as 19, 27, 29 and 30, the electron withdrawing ability was more efficient than symmetric dienophiles. Dienophiles of 4-vinyl pyridine group(30,32) were more reactive than that of 2-vinyl pyridine group(29,31). This reaction also could be carried out by photoreaction as well as direct thermal reaction. Eventhaugh we observed no reaction between 6 and (C3S5)n by direct thermal method, it yielded some cycloadduct via photoreaction even in very low yield. The cycloadducts, EDT-DTT derivatives, were converted to EDT-DTO derivatives using Hg(OAc)2 in CHCI3. The EDT-DTT(O) DERIVATIVES can be good can-didates as precursors to organic electronic materials.