• Macromolecular Research
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• 제12권3호
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• pp.322-324
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• 2004

Poly(1-dodecyl-2,5-pyrrylene vinylene) (PDPV) has an extended 1t-conjugated structure and exhibits characteristic spectroscopic features. The PDPV we prepared has an absorption maximum at 510nm and its long absorption tail at ca. 750nm in methylene chloride is due to the long 1t-conjugated system connected to vinyl group. The large red-shift of emission was 625nm upon excitation at 480nm, which suggests the existence of a low emissive state. The emission of PDPV in less-polar solvents decreased markedly relative to that in the more-polar solvents; this observation was ascribed possibly to quenching by a strong vibrational mode of the dodecyl groups of PDPV in less-polar solvents. Furthermore, the emission from the high-energy side had a single decay component (0.1㎱, 49.96%), while that from the low-energy side had two components (0.6㎱, 27.1 %; 2.7㎱, 22.87%). We characterized the redox properties of PDPV by cyclic voltammetry. Every redox peak showed irreversible behavior; the oxidation peaks appeared at 1.7,0.8, and 0.6V and the reduction peak at -0.5V.

• Bulletin of the Korean Chemical Society
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• 제12권2호
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• pp.163-169
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• 1991

The photochemical and photophysical properties of N-(2-haloarylmethyl)pyridinium, N-(arylmethyl)-2-halopyridinium, N-(2-haloarylmethyl)-2-halopyridinium salts and N-(2-halobenzyl)-isoquinolinium salt are studied. The pyridinium salts photocyclize to afford isoindolium salts, while the isoquinolium salts do not. In the photocyclization of N-(2-chlorobenzyl)-2-chloropyridinium salts, pyrido[2,1-a]-4-chloroisoindolium salt is formed by the cleavage of chlorine of pyridinium ring. This indicates that the excited moiety is not the phenyl ring, but the pyridinium ring. The triplet states of the pyridinium salts are believed to be largely involved in the photocyclization, since oxygen retards most of the reaction. Some assistance of a ${\pi}$-complex between the excited chlorine moiety of the salt and phenyl plane of the same molecule is required to explain the reactivity of the salts. N-(Benzyl)-2-chloropyridinium salt is two times more reactive than N-(2-chlorobenzyl)pyridinium salt. N-(Benzyl)-2-chloropyridinium salt can form ${\pi}-complex$ effectively because of the electron-rich phenyl group. The ${\pi}$-complex affords an intermediate, phenyl radical by cleaving the chlorine atom. The photocyclized product, isoindolium salt is obtained by losing the hydrogen atom from the phenyl radical. The reactive pyridinium salts 1a, 2a and 3a have a low fluorescence quantum yield (${\Phi}F$ < 0.01) and a higher triplet energy (ET > 68 kcal/mole) than the unreactive quinolinium salt. The unreactivity of isoquinolinium salt can be understood in relation to its high fluorescence quantum yield and its low triplet energy $(E_T = 61 kcal/mole).$.

• 공업화학
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• 제34권6호
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• pp.633-639
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• 2023

We synthesized 2-(10-methyl-10H-phenothiazin-3-yl)-5-phenyl-1,3,4-oxadiazole (MPPO) and 5,5-(10-methyl-10H-phenothiazin-3,7-diyl)-bis-(2-phenyl-1,3,4-oxadiazole) (DPPO). MPPO has both electron-donating and electron-accepting substituents with asymmetric molecular geometry. By incorporating one extra electron-accepting group into MPPO, we created a symmetric molecule, which is DPPO. The optical and electrochemical properties of these compounds were measured. The lowest unoccupied molecular orbital (LUMO) level of DPPO was lower than that of MPPO. The excited-state dipole moment of DPPO, with symmetric geometry, was calculated to be 4.1 Debye, whereas MPPO, with asymmetric geometry, had a value of 7.0 Debye. The charge-carrier mobility of both compounds was similar. We fabricated non-doped organic light-emitting diodes (OLEDs) using D-A type molecules as an emitting layer. The current efficiency of the DPPO-based device was 7.8 cd/A, and the external quantum efficiency was 2.4% at 100 cd/m², demonstrating significantly improved performance compared to the MPPO-based device. The photophysical and electroluminescence (EL) characteristics of the two D-A type molecules showed that molecular symmetry, as well as the lowered LUMO level of DPPO, played critical roles in the enhancement of EL performance.

• 한국해양환경ㆍ에너지학회지
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• 제16권1호
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• pp.53-59
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• 2013

1990년대 이후, 중소형 폐 선박으로부터 생성되는 FRP를 재활용하기 위한 방법으로 층상으로 배열된 로빙층과 매트층을 분리하는 것은 친 환경적이면서도 경제적 재활용의 장점을 가지고 있다. 그러나 효율적으로 로빙층과 매트층을 분리하는 기술과 로빙층은 매트층에 비해 얇은 두께로 존재한다는 이유로 인해 로빙층을 매트층과 분리할 때 기계가 자동적으로 층간의 차이를 인식하는 방법은 아직 개발이 이루지지 않고 있다. 본 연구에서는 유리의 구성비가 다른 두 층의 화학적 성질의 차를 이용하여 광학적으로 층간 인식이 가능한 방법을 모색하였다. 또한 다양한 로빙층의 구성에도 자동적으로 절단위치를 분석하는 절단시스템과 최종생산물의 유용성을 확보할 수있는 다양한 크기의 유리섬유를 생산할 수있는 세단기를 개발하였다. 본 연구 결과로 광학적 인식기술과 유연한 절단기술 그리고 다양한 세단기술이 융합된 폐 FRP의 분리 공정의 단순화와 자동화를 달성하게 되었다.

• Bulletin of the Korean Chemical Society
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• 제24권4호
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• pp.446-452
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• 2003

Some new nanohybrid materials have been synthesized by intercalating the oxotitanium(IV) meso-tetrakis(4- sulfonatophenyl) porphyrin$(O=Ti^{(IV)} TSPP)$ into the Zn/Al layered double hydroxides (LDHs), and their structures and photophysical properties have been investigated by various laser spectroscopic techniques. According to the XRD pattern of the synthesized nanohybrid materials, the macrocycle plane of $O=Ti^{(IV)}$ TSPP are grafted perpendicular to the LDH layers. The $O=Ti^{(IV)}$ TSPP-intercalated LDH exhibits band broadening of the absorption spectrum and a blue shift of Q-band as compared to that observed in solution. Resonance Raman spectral measurements demonstrate that the positively charged LDHs give rise to a slight decrease of the electronic density of the porphyrin ring accompanying a small change of the electronic distribution of the $O=Ti^{(IV)}$ TSPP. Consequently the LDH environment affects the energies of the two highest occupied molecular orbitals (HOMOs) of the $O=Ti^{(IV)}$) TSPP, $a_{1u}$ and $a_{2u}$, producing a mixed orbital character. Being consistent with these electronic structural changes of $O=Ti^{(IV)}$ TSPP in LDH, both the fluorescence spectral change and the fsdiffuse reflectance transient measurements imply that the photoexcitation of the $O=Ti^{(IV)}$ TSPP intercalated into LDH undergoes fast relaxation to the O=Ti(IV) $TSPP^+-LDH^- $charge transfer (CT) state within a few picoseconds, followed by a photoinduced electron transfer between the O=Ti(IV) TSPP and LDHs with a rate constant greater than %1×10^{10}S^{-1}$. No evidence is found for back electron transfer. In conclusion, the $O=Ti^{(IV)}$ TSPP intercalated LDH seems to be a possible candidate for an artificial reaction center for an efficient solar energy conversion system.

• 청정기술
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• 제21권2호
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• pp.102-107
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• 2015

Rhodamine염료는 높은 흡광계수와 함께 넓은 가시광선 영역에서 고효율과 안정성을 나타내는 형광을 제공함으로써 형광표지 물질로 널리 사용되고 있다. Rhodamine 화합물을 형광표지 물질로 이용하기 위해서는 rhodamine골격을 (생체)분자나 표면에 공유결합 시키는 화학적 과정이 필수적이기 때문에 이에 관련하여 다양한 rhodamine유도체를 합성해내는 효율적이고 실제적인 방법의 개발은 큰 관심을 끌어왔다. Sulforhodamine B는 반응성이 큰 두 개의 sulfoxy작용기를 포함하고 있는데 이를 이용하여 여러 재료에 공유결합 시킴으로써 널리 활용될 수 있는 유용한 화합물이다. 본 연구에서는 4-formyl-1, 3-benzenedisulfonic acid의 disodium염과 3-diethylaminophenol으로부터 3단계에 걸쳐 sulforhodamine B를 합성하는 과정을 연구하였다. 이 과정에서 dihydroxytriarylmethane 중간체를 xanthene 골격으로 전환하는 두 번째 단계를 획기적으로 개선하는 방법에 대해 기술하였다. 이는 반응 중에 생성되는 물분자가 역반응에 참여하는 것을 억제하도록 메탄올을 가함으로써 이루어졌다. 그 결과, 반응온도는 낮아지고(135에서 80 ℃), 수율은 크게 증가되었다(20% 미만에서 84%). 이로써, 기존의 3단계에 걸친 sulforhodamine B의 제법은 에너지 절감 및 자원효율 면에서 개선된 방법으로 이루어지게 되었다.

• Rapid Communication in Photoscience
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• 제1권1호
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• pp.1-9
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• 2012

Luminescent lanthanide complexes have been overviewed for advanced photonics applications. Lanthanide(III) ions ($Ln^{3+}$) were encapsulated by the luminescent ligands such as metalloporphyrins, naphthalenes, anthracene, push-pull diketone derivatives and boron dipyrromethene(bodipy). The energy levels of the luminescent ligands were tailored to maintain the effective energy transfer process from luminescent ligands to $Ln^{3+}$ ions for getting a higher optical amplification gain. Also, key parameters for emission enhancement and efficient energy transfer pathways for the sensitization of $Ln^{3+}$ ions by luminescent ligands were investigated. Furthermore, to enhance the optophysical properties of novel luminescent $Ln^{3+}$ complexes, aryl ether-functionalized dendrons as photon antennas have been incorporated into luminescent $Ln^{3+}$ complexes, yielding novel $Ln^{3+}$-cored dendrimer complex such as metalloporphyrins, naphthalenes, and anthracenes bearing the Fr$\acute{e}$chet aryl-ether dendrons, namely, ($Er^{3+}-[Gn-Pt-Por]_3$ (terpy), $Er^{3+}-[Gn-Naph]_3$(terpy) and $Er^{3+}-[Gn-An]_3$(terpy)). These complexs showed much stronger near-IR emission bands at 1530 nm, originated from the 4f-4f electronic transition of the first excited state ($^4I_{13/2}$) to the ground state ($^4I_{15/2}$) of the partially filled 4f shell. A significant decrease in the fluorescence of metalloporphyrins, naphthalenes and anthracene ligand were accompanied by a strong increase in the near IR emission of the $Ln^{3+}$ ions. The near IR emission intensities of $Ln^{3+}$ ions in the lanthanide(III)-encapsulated dendrimer complexes were dramatically enhanced with increasing the generation number (n) of dendrons, due to the site-isolation and the light-harvesting(LH) effects. Furthermore, it was first attempted to distinguish between the site-isolation and the light-harvesting effects in the present complexes. In this review, synthesis and photophysical studies of inert and stable luminescent $Ln^{3+}$ complexes will be dealt for the advanced photonics applications. Also, the review will include the exploratory investigation of the key parameters for emission enhancement and the effective energy transfer pathways from luminescent ligands to $Ln^{3+}$ ions with $Ln^{3+}$-chelated prototype complexes.

• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.758-764
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• 2014

Femtosecond vibrational spectroscopy was used to measure the vibrational population relaxation time ($T_1$) of different anions bound to ferric myoglobin ($Mb^{III}$) and hemoglobin ($Hb_{III}$) in $D_2O$ at 293 K. The $T_1$ values of the anti-symmetric stretching (${\nu}_1$) mode of NCS in the $NCS^-$ bound to $Mb^{III}$ ($Mb^{III}$NCS) and $Hb_{III}$ ($Hb_{III}$NCS) in $D_2O$ are $7.2{\pm}0.2$ and $6.6{\pm}0.2$ ps, respectively, which are smaller than that of free NCS. in $D_2O$ (18.3 ps). The $T_1$ values of the ${\nu}_1$ mode of NCO in the $NCO^-$ bound to $Mb^{III}$ ($Mb^{III}$NCO) and $Hb_{III}$ ($Hb_{III}$NCO) in $D_2O$ are $2.4{\pm}0.2$ and $2.6{\pm}0.2$ ps, respectively, which are larger than that of free $NCO^-$ in $D_2O$ ($1.9{\pm}0.2$ ps). The smaller $T_1$ values of the ${\nu}_1$ mode of the heme-bound NCS suggest that intramolecular vibrational relaxation (VR) is the dominant relaxation pathway for the excess vibrational energy. On the other hand, the longer $T_1$ values of the ${\nu}_1$ mode of the heme-bound NCO suggest that intermolecular VR is the dominant relaxation pathway for the excess vibrational energy in the ${\nu}_1$ mode of $NCO^-$ in $D_2O$, and that intramolecular VR becomes more important in the vibrational energy dissipation of the ${\nu}_1$ mode of NCO in $Mb^{III}$NCO and $Hb_{III}$NCO.

• 폴리머
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• 제25권2호
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• pp.199-207
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• 2001

본 연구에서는 경화촉진제로서 N,N-dimethyl benzyl amine (BDMA) 또는 1-cyanoethyl-2-ethyl-4-methyl imidazole (2E4MZ-CN)을 포함하고 있는 산무수물계 경화제에 의한 diglycidyl ether of bisphenol-A (DGEBA)의 경화거동을 형광분석기를 사용하여 광물리적 특성 변화의 관점에서 해석하였다. 이를 위해 1,3-bis-(1-pyrene)propane (BPP) probe를 에폭시수지 내에 균일하게 도입시켰다. 주위 환경 겔화에 의한 분자의 공간구조 변화에 민감한 BPP probe는 분자내 여기체 형광을 잘 형성하였으며 에폭시수지의 경화반응에 따른 미세점도 변화 또는 분자의 움직임에 민감하였다. 에폭시수지의 경화거동은 경화시간, 경화온도 및 경화촉진제의 종류에 따른 단량체 형광세기 ($I_{M}$ ), 여기체 형광세기 ($I_{E}$ ) 그리고 $I_{M}$ /$I_{E}$ 값의 변화로부터 설명되었다. 그 결과는 이전의 DSC 또는 torsion pendulum을 이용하여 에폭시-산무수물계에 대하여 얻어진 경화거동 결과와 일치하였다. 또한, 형광분석 방법은 다른 분석 방법에서 해석이 어려운 저온영역에서의 열경화성 수지의 경화거동에 대한 정보를 제시하였다.

• 한국염색가공학회:학술대회논문집
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• 한국염색가공학회 2010년도 제3회 국제학회
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• pp.40-40
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• 2010

Studies on attractive color changing property of dye chromophore and fluorophore have been greatly enjoyed in the related industrial and research fields such as optoelectronics, chemosensor, biosensor and so on. The optical property based on D-$\Pi$-A intramolecular charge transfer (ICT) system of chromophore molecules can be utilized as suitable sensing probes for checking media polarity and determining colorimetric chemosensing effect, especially heavy metal detection. These finding are obtained by absorption and emission properties. In this work, donor-acceptor D-$\Pi$-A type fluorescent dyes were designed and synthesized with the corresponding donor and acceptor groups. The selected donor moieties might be provided prominent amorphous properties which are very useful in designing and synthesizing functional polymers and in fabricating devices. Another reasons to choose are commercial availabilities in high purity and low price. Donor-bridge-acceptor (D-A) type dyes can produce impressive optical-physical properties, yielding them potentially suitable for applications in the synthesis of small functional organic molecules. Small organic functional molecules have unique advantages, such as better solubility, amorphous character, and represent an area of research which needs to be explored and developed. Currently, their applications in metalorganic compounds is rapidly expanding and becoming widespread in self-assembly processes, photoluminescence applications, chiral organocatalysts, and ingrafts with nanomaterials. Colloidal nanoparticles have received great attentions in recent years. The photophysical properties of nanoparticles, particularly in terms of brightness, photostability, emission color purity and broad adsorption range, are very attractive functions in many applications. To our knowledge background, colloidal nanoparticles have been enjoyed their applications in bio-probe research fields. This research interest can be raised by the advantages of the materials such as high photoluminescence quantum yields, sharp emission band, long-term photostability and broad excitation spectra. In recent, the uses of nanoparticles being embedded in a polymer matrix and binded on polymer surface have been explored and their properties such as photo-activation and strong photoluminescence have been proposed. The prepared chromophores and nanoparticles were investigated with absorption and emission properties, solvatochromic behaviors, pH induced color switching effects, chemosensing effects and HOMO/LUMO energy potentials with computer simulation. In addition, synthesized fluorophore dyes and particles were applied onto PE/Aramid fiber fluorescing colorations. And the related details were then discussed.