• Bulletin of the Korean Chemical Society
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• v.35 no.4
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• pp.1121-1127
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• 2014

The design, synthesis, and structural characterization of two new palladium complexes based on Schiff base ligands is reported; $[Pd(L1)_2]$ (1) and $[Pd(L2)_2]$ (2), [HL1 = 2-((E)-(2,6-diethylphenylimino)methyl)-4,6-dibromophenol, L2 = (E)-N-benzylidene-2,6-diethylbenzenamine], which are obtained by functionalizing Schiff base ligands with or without electron-withdrawing groups. Both compounds are mononuclear structures. Comparisons are made to the compounds 1 and 2 to analyze and understand the effect of electron-withdrawing groups. Antibacterial activity studies indicate the electron-withdrawing groups on Schiff base ligands enhance antibacterial activity. Catalytic activity, however, is reduced due to the enhanced steric-hindrance of the electron-withdrawing groups. Electronic absorption and emission properties of HL1, L2, 1 and 2 are also reported.

• Journal of Photoscience
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• v.11 no.1
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• pp.7-9
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• 2004

The synthesized macrocycle L was found to be a smart fluorescent receptor which distinguishable efficiently from various neutral molecules with the functional groups such as the electron donating (X =$CH_3$, N($CH_3$)$_2$ and O$CH_3$) and electron withdrawing groups (X =F and Cl), respectively. In the case of guest molecules containing electron donating groups, the fluorescence of macrocycle L was enhanced in the presence of the guest molecules. On the contrary, in the case of guest molecules containing electron withdrawing groups, it was almost quenched in the presence of those.

• Proceeding of EDISON Challenge
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• 2017.03a
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• pp.165-171
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• 2017

Diels-Alder 반응은 고리형 탄소화합물을 만드는 유기 합성 과정에서 매우 중요한 반응이다. 이 반응은 중간생성물 없이 오직 1 step으로 진행되는데, diene이나 dienophile에 결합한 치환기의 electron donating 및 electron withdrawing 성질에 따라 반응성이 달라진다고 알려져 있다. 이 때 반응물인 diene과 dienophile의 분자 오비탈 및 전이 상태의 에너지 변화를 계산화학을 통해 분석한다면 Diels-Alder 반응을 보다 심도 있게 이해할 수 있다. 이에 따라 본 연구에서는 DFT 계산을 통하여 치환기에 따른 활성화 에너지의 크기와 diene의 nucleophilicity 및 dienophile의 electrophilicity를 비교하였다. 이를 통해 electron withdrawing group의 경우 분자의 electrophilicity를 증가시키고, electron donating group의 경우 nucleophilicity를 증가시킨다는 것을 확인할 수 있었다. 그 결과, Diels-Alder 반응이 일어날 때 dienophile의 경우 치환된 electron withdrawing group에 의해 electrophilicity가 증가함에 따라 활성화 에너지가 낮아져 반응이 잘 일어나고, 반대로 diene의 경우 electron donating group이 치환되어 있을 때 nucleophilicity의 증가에 따라 반응이 잘 일어난다는 것을 알 수 있었다.

• Macromolecular Research
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• v.15 no.3
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• pp.216-220
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• 2007

A new polyfluorene-based copolymer having 2-ethylhexyloxy-5-methoxy-l,4-phenylene as an electron donating group and 2,5-diphenyl-oxadiazole as an electron withdrawing group was synthesized by the Suzuki coupling reaction. The obtained copolymer was characterized by $^1H-NMR,\;^{13}C-NMR$, and IR-spectroscopy. The weight average molecular weight ($M_w$) of the obtained polymer was 18,600 with a polydispersity index of 1.5. The maximum photoluminescence of the solution and film of the polymer was observed at 453 nm and 456 nm, respectively. A double-layer device with the configuration, ITO/PEDOT/copolymer/Al, emitted blue light at 460 nm.

• Journal of the Korean Chemical Society
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• v.67 no.3
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• pp.175-180
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• 2023

Tetra-aryl substituted A4-type porphyrins (TP, TD, TA) and trans-A2B2 porphyrins (DDP1, AAP1) with electron-donating or withdrawing groups were synthesized. The band gap energy of those porphyrins was calculated from their UV-Vis spectra and CV data. With an electron-withdrawing group, the band gap energy of porphyrin TA increased via the LUMO energy up. Meanwhile, the introduction of an electron-donating group decreased the band gap of porphyrin by HOMO level up as as in the case of porphyrin TD. The band gap (2.19-2.28 eV) of metalloporphyrin PP-Ni was greater than those (1.81-2.06 eV) of non-metalloporphyrins PP due to the LUMO level up.

• Journal of the Korean Chemical Society
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• v.45 no.3
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• pp.207-212
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• 2001

DFT calculations have been performed on several substituted 1,4-diaza-1,3-butadienes (1,4-DABs) with electron donating and withdrawing groups at the terminal two nitrogens to investigate the reactivity of Diels-Alder reaction with acrolein. The calculated FMO (Frontier Molecular Orbital) energies for the optimized 1,4-disubstituted-1,4-DABs have been used to explain both normal and inverse electron demand Diels-Alder reactions. It is shown that the electron donating and withdrawing substituents lead to the normal(HOMO diene controlled) and inverse electron demand (LUMO diene controlled) Diels-Alder reactions, respectively.

• Bulletin of the Korean Chemical Society
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• v.28 no.8
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• pp.1363-1370
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• 2007

The geometrical structures of pyridazin-3-one derivatives (4,5-dihalopyridazin-3-one and 4-halo-5- alkoxypyridazin-3-one) with various functional and substituent groups were fully optimized using the ab initio Hartree-Fock (HF) and second order Moller-Plesset perturbation (MP2) methods. At the N2-, C4-, and C5- positions on the pyridazin-3-one rings, the structural and electronic features pertaining to the variations of the functional and substituent groups were analyzed, respectively. The trends in the variation of the bond lengths, atomic charges, and energetics (relative energy, binding energy) of the derivatives induced by changing the electron donating functional groups (X1 = OMe, OEt) to electron withdrawing groups (X1 = Cl, NO2) were examined. The variations of the bond lengths, atomic charges, and binding energies with the electron withdrawing strength of the substituent groups (Y = Me → F) were also investigated.

• Applied Chemistry for Engineering
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• v.23 no.6
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• pp.539-545
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• 2012

3-(2-benzotriazolovinyl)thiophene (BVT) was synthesized by the connection of the thiophene with the electron-withdrawing group, benzotriazole, through the vinylene. Its structure was confirmed by FT-IR, $^1H$-NMR, $^{13}C$-NMR and 2D hetero-cosy spectroscopy. Both BVT and 3-octylthiophene (OT) were copolymerized and showed an average molecular weight of 12000 (PDI 2.67) and 15000 (PDI 2.55), respectively. The copolymers were dissolved in the organic solvent such as chloroform, THF, TCE, etc. The mole ratios of BVT and OT in the synthesized copolymers were confirmed as 1 : 1.8 and 1 : 2.8 from $^1H$-NMR spectra. The UV-vis maximum absorption of copolymers appeared at the wavelength of 470 nm and 465 nm and the photoluminescence at ${\lambda}_{max}$ = 662 nm and 641 nm correspond to red-orange light. The band gaps of copolymers at 1.96 eV and 2.02 eV were found to be higher than those of poly(3-octylthiophene). The HOMO energy levels of the copolymers decreased overall in comparison with those of poly(3-octylthiophene), but the overall LUMO energy level increased.

• Bulletin of the Korean Chemical Society
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• v.16 no.12
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• pp.1203-1208
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• 1995

Theoretical studies of the effect of the nonleaving group (RY) on the breakdown mechanism of the tetrahedral anionic intermediate, T-, formed by the addition of a less basic phenoxide nucleophile (X) to phenyl benzoates with a more basic phenoxide leaving group (Z) have been carried out using the PM3 MO method. The identity acyl transfer reactions (X=Z) are facilitated by an electron-withdrawing RY whereas they are inhibited by an electron-donating RY group. The results of non-identity acyl transfer reactions indicate that a more electron-donating RY group leads to a greater lowering of the higher barrier, TS2, with a greater degree of bond cleavage, and a greater negative charge development on the phenoxide oxygen atom, whereas the opposite is true for a more electron-withdrawing RY group, i.e., leads to a greater lowering of the lower barrier, TS1. The results provide theoretical basis for the signs of ρXY(>0) and ρYZ(<0) observations.

• 한국정보디스플레이학회:학술대회논문집
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• 2009.10a
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• pp.762-766
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• 2009

We have synthesized and demonstrated a red emission in Organic Light Emitting Diodes (OLEDs) using phosphorescent iridium(III) complexes based on the 2-phenylpyridine ligands with electron-withdrawing carbonyl groups. Among those, a device exhibited highly efficient red-orange emission with the luminance of 20460 cd/$m^2$ at 12 V, the luminous efficiency of 22.0 cd/A at 20 mA/$cm^2$, and the $CIE_{x,y}$ coordinates of (x=0.560, y=0.439 ) at 10 V.