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최태진,장지영 한국고분자학회 2016 Macromolecular Research Vol.24 No.11
Thermochromic polymer nanocomposite films were prepared from polymerizable organogels. Organogelator 1 had a structure which 3,4,5-tris(ω-decenyl)benzamide groups were attached to a quarterthiophene core through amide bonds. Organogelator 2 had the same structure except that tris(ω-decenyl) groups were replaced by tris(n-decanyl) groups. The PMMA nanocomposite films were prepared by the photopolymerization of the organogels formed in methyl methacrylate (MMA). The film containing 1 (0.5 wt%) showed reversible thermochromism. The emission under 365 nm irradiation was changed to bright green from orange by heating up to 120 oC and returned to its initial orange by cooling. To the contrary, the PMMA composite film prepared from the organogel of 2 (0.5 wt%) did not show a reversible thermochromic property. Organogelator 1 with polymerizable terminal vinyl groups was covalently embedded in the PMMA matrix, but 2 was not. The reversible thermochromism was likely caused by the thermally reversible conformational change of quarterthiophene units in the polymer fibers.
최태진,장지영 한국고분자학회 2016 Macromolecular Research Vol.24 No.12
Thermochromic polymer nanocomposite films were prepared from polymerizable organogels. Organogelator 1 had a structure which 3,4,5-tris(ω-decenyl)benzamide groups were attached to a quarterthiophene core through amide bonds. Organogelator 2 had the same structure except that tris(ω-decenyl) groups were replaced by tris(n-decanyl) groups. The PMMA nanocomposite films were prepared by the photopolymerization of the organogels formed in methyl methacrylate (MMA). The film containing 1 (0.5 wt%) showed reversible thermochromism. The emission under 365 nm irradiation was changed to bright green from orange by heating up to 120 oC and returned to its initial orange by cooling. To the contrary, the PMMA composite film prepared from the organogel of 2 (0.5 wt%) did not show a reversible thermochromic property. Organogelator 1 with polymerizable terminal vinyl groups was covalently embedded in the PMMA matrix, but 2 was not. The reversible thermochromism was likely caused by the thermally reversible conformational change of quarterthiophene units in the polymer fibers.
S· · ·S Interaction in Pd(II) Complexes of Bis(phosphino)oligothiophene with Various Substituents
Arooj, Mahreen,Kim, Kyeong-Hyeon,Kim, Dong-Hwan,Kim, Byung-Sun,Park, Gye-Young,Jeong, Si-Hwa,Shin, Sung-Chul,Park, Jong-Keun Korean Chemical Society 2009 Bulletin of the Korean Chemical Society Vol.30 No.12
Park, Kyu Hyung,Kim, Pyosang,Kim, Woojae,Shimizu, Hideyuki,Han, Minwoo,Sim, Eunji,Iyoda, Masahiko,Kim, Dongho WILEY‐VCH Verlag 2015 Angewandte Chemie Vol.127 No.43
<P><B>Abstract</B></P><P>Excited‐state dynamic planarization processes play a crucial role in determining exciton size in cyclic systems, as reported for π‐conjugated linear oligomers. Herein, we report time‐resolved fluorescence spectra and molecular dynamics simulations of π‐conjugated cyclic oligothiophenes in which the number of subunits was chosen to show the size‐dependent dynamic planarization in the vicinity of a ring‐to‐linear behavioral turning point. Analyses on the evolution of the total fluorescence intensity and the ratio between 0–1 to 0–0 vibronic bands suggest that excitons formed in a cyclic oligothiophene composed of six subunits fully delocalize over the cyclic carbon backbone, whereas those formed in larger systems fail to achieve complete delocalization. With the aid of molecular dynamics simulations, it is shown that distorted structures unfavorable for efficient exciton delocalization are more easily populated as the size of the cyclic system increases.</P>
Choi, Yoon-Suk,Lee, Woo-Hyung,Kim, Jae-Ryoung,Lee, Sang-Kyu,Shin, Won-Suk,Moon, Sang-Jin,Park, Jong-Wook,Kang, In-Nam Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.2
A series of new quinoxaline-based thiophene copolymers (PQx2T, PQx4T, and PQx6T) was synthesized via Yamamoto and Stille coupling reactions. The $M_ws$ of PQx2T, PQx4T, and PQx6T were found to be 20,000, 12,000, and 29,000, with polydispersity indices of 2.0, 1.2, and 1.1, respectively. The UV-visible absorption spectra of the polymers showed two distinct absorption peaks in the ranges 350 - 460 nm and 560 - 600 nm, which arose from the ${\pi}-{\pi}^*$ transition of oligothiophene units and intramolecular charge transfer (ICT) between a quinoxaline acceptor and thiophene donor. The HOMO levels of the polymer ranged from -5.37 to -5.17 eV and the LUMO levels ranged from -3.67 to -3.45 eV. The electrochemical bandgaps of PQx2T, PQx4T, and PQx6T were 1.70, 1.71, and 1.72 eV, respectively, thus yielding low bandgap behavior. PQx2T, PQx4T, and PQx6T had open circuit voltages of 0.58, 0.42, and 0.47 V, and short circuit current densities of 2.9, 5.29 and 9.05 mA/$cm^2$, respectively, when $PC_{71}BM$ was used as an acceptor. For the solar cells with PQx2T-PQx6T:$PC_{71}BM$ (1:3) blends, an increase in performance was observed in going from PQx2T to PQx6T. The power conversion efficiencies of PQx2T, PQx4T, and PQx6T devices were found to be 0.69%, 0.73%, and 1.80% under AM 1.5 G (100 mW/$cm^2$) illumination.
Hayakawa Teruaki,Kouketsu Takayuki,Kakimoto Masa-alki,Yokoyama Hideaki,Horiuchi Shin The Polymer Society of Korea 2006 Macromolecular Research Vol.14 No.1
A novel fabrication of the patterned surfaces in the polymer films was demonstrated by using the self-organizing character of the block copolymers of polystyrene-b-oligothiophenes and polystyrene-b-aromatic amide dendron. Hexagonally arranged open pores with a micrometer-size were spontaneously formed by casting the polymer solutions under a moist air flow. The amphiphilic character of the block copolymers played the crucial role as a surfactant to stabilize the inverse emulsion of water in the organic solvent, and subsequently the aggregated structure of the hydrophilic oligothiophene or aromatic amide dendron segments remained on the interiors of the micropores. The chemical composition on the top of the surface of the microporous films was characterized by energy-filtering transmission electron microscopy (EFTEM) or a time-of-flight secondary ion mass spectrometer (ToF-SIMS). The characterizations clearly indicated that the patterned surfaces in the self-organized block copolymer films with the hexagonally ordered microporous structures were fabricated in a single step.
Ryu, Tae-In,Song, Myung-Kwan,Lee, Myung-Jin,Jin, Sung-Ho,Kang, Sun-Woo,Lee, Jin-Yong,Lee, Jae-Wook,Lee, Chan-Woo,Gal, Yeong-Soon Korean Chemical Society 2009 Bulletin of the Korean Chemical Society Vol.30 No.10
Three heteroleptic ruthenium sensitizers, Ru(L)($L^1)(NCS)_2$ [L = 4,4'-dicarboxylic acid-2,2'-bipyridine, Ru-T1: $L^1$ = (E)-2-(4'-methyl-2,2'-bipyridin-4-yl)-3-(thiophen-2-yl)acrylonitrile, Ru-T2: $L^2$ = (E)-3-(5'-hexyl-2,2'-bithiophen-5- yl)-2-(4'-methyl-2,2'-bipyridin-4-yl)acrylonitrile, and Ru-T3: $L^3$ = (E)-3-(5"-hexyl-2,2':5',2"-terthiophen-5-yl)-2- (4'-methyl-2,2'-bipyridin-4-yl)acrylonitrile)], were synthesized and used as photosensitizers in nanocrystalline dyesensitized solar cells (DSSCs). The introduction of the 3-(5-hexyloligothiophen-5-yl)acrylonitrile group increased the conjugation length of the bipyridine donor ligand and thus improved their molar absorption coefficient and light harvesting efficiency. DSSCs with the configuration of Sn$O_2$: F/Ti$O_2$/ruthenium dye/liquid electrolyte/Pt devices were fabricated using these Ru-$T1{\sim}T3$ as a photosensitizers. Among the devices, the DSSCs composed of Ru-T2 exhibited highest power conversion efficiency (PCE) of 2.84% under AM 1.5 G illumination (100 mW/$cm^2$).
Tae In Ryu,송명관,Myung Jin Lee,진성호,Sunwoo Kang,이진용,이재욱,Chan Woo Lee,제갈영순 대한화학회 2009 Bulletin of the Korean Chemical Society Vol.30 No.10
Three heteroleptic ruthenium sensitizers, Ru(L)(L1)(NCS)2 [L = 4,4'-dicarboxylic acid-2,2'-bipyridine, Ru-T1: L1 =(E)-2-(4'-methyl-2,2'-bipyridin-4-yl)-3-(thiophen-2-yl)acrylonitrile, Ru-T2: L2 = (E)-3-(5'-hexyl-2,2'-bithiophen-5-yl)-2-(4'-methyl-2,2'-bipyridin-4-yl)acrylonitrile, and Ru-T3: L3 = (E)-3-(5"-hexyl-2,2':5',2"-terthiophen-5-yl)-2-(4'-methyl-2,2'-bipyridin-4-yl)acrylonitrile)], were synthesized and used as photosensitizers in nanocrystalline dyesensitized solar cells (DSSCs). The introduction of the 3-(5-hexyloligothiophen-5-yl)acrylonitrile group increased the conjugation length of the bipyridine donor ligand and thus improved their molar absorption coefficient and light harvesting efficiency. DSSCs with the configuration of SnO2: F/TiO2/ruthenium dye/liquid electrolyte/Pt devices were fabricated using these Ru-T1∼T3 as a photosensitizers. Among the devices, the DSSCs composed of Ru-T2 exhibited highest power conversion efficiency (PCE) of 2.84% under AM 1.5 G illumination (100 mW/cm2).