• 대한화학회지
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• 제23권5호
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• pp.277-285
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• 1979

비선형 Hammett 관계를 고찰하기 위해서 $XC_6H_4CH_2Cl\;(X=H,\;p=CH_3,\;p-NH_2,\;p-NO_2)$와 benzyl radical, cation, anion에 대해서 CNDO/2 계산을 행하였다. 이로부터 얻은 주요 결론은 다음과 같다. 1. 염화벤질은 C-Cl 결합과 고리의 $\pi$-system 간의 ${\sigma}-{\pi}$ conjugation으로 기인되는 borderline 성질을 나타내고 있다. 2. Mutual conjugation의 정도는 $\pi$-charge와 bond alternation, 그리고 interfrontier level separation narrowing 효과로 확인된다. 3. 전자공여 파라치환체는 벤질탄소의 HOMO AO 계수를 감소시키는 반면, 전자흡인 파라치환체는 벤질탄소의 LUMO AO 계수를 감소시킨다.

• 대한화학회지
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• 제14권1호
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• pp.1-4
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• 1970

The methyl group does not possess an unshared pair of electrons. But F.A. Matsen has introduced the concept of the methyl group as a Pseudo-heteroatom which contributes a pair of electrons to ${\pi}$ system. In this heteroatom model, A. Streitwieser et al have assumed that the electrons in a methyl group behave to their approximation as a single electron pair on a single atom. But the theoretical basis on the heteroatom model hyper-conjugation has not studied yet. In this paper, Linear combination of Bond orbital and group theory is used to investigate the theoretical basis for it.

• Bulletin of the Korean Chemical Society
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• 제22권12호
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• pp.1316-1322
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• 2001

Transition metal complexes of novel mono- and di-ferrocene-substituted porphyrins have been synthesized and characterized by structural and electrochemical methods. The X-ray structures of Mn(FPTTP)Cl and Mn(DFTTP)Cl showed the distorted square pyramidal coordination geometry with syn configuration of chloride and ferrocenyl substituents. The electrochemistry of ferrocene-substituted porphyrins and their metal complexes has been determined to elucidate the ${\pi}-conjugation$ effect of the porphyrin ring. The ferrocenyl group of H2FPTTP underwent a reversible one-electron transfer process at 0.30 V, indicating the good electron donating effect of the phorphyrin ring to the ferrocene substituent. The redox potential of the ferrocenyl subunit and porphyrin ring was affected by the central metal ions of the metalloporphyrins, that is, Zn(II) and Ni(II) made the oxidation of ferrocene much easier and Mn(III) made it harder. The ferrocene subunits of H2DFTTP interacted electrochemically with each other with peak splitting of 0.21 V. The strength of the electrochemical interactions between the two ferrocenyl substituents can be controlled by central metal ions of metalloporphyrins.

• 대한화학회지
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• 제56권3호
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• pp.313-315
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• 2012

• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2247-2248
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• 2013

• Bulletin of the Korean Chemical Society
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• 제23권2호
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• pp.281-285
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• 2002

The photophysical properties and the singlet oxygen generation efficiencies of meso-tetraphenyl-trithiasapphyrin $(S_3TPS)$ and meso-tetmkis(p-methoxy phenyl)-trithiasapphy rin ((p-MeO)-$S_3TPS$) have been investigated, utilizing steady-state and time-resolved spectroscopic methods to elucidate the possibility of their use as photosensitizers for photodynamic therapy (PDT). The observed photophysical properties were compared with those of other porphyrin-like photosensitizers in geometrical and electronic structural aspects, such as extended ${\pi}$ conjugation, structural distortion, and internal heavy atoms. The steady-state electronic absorption and fluorescence spectra were both red-shifted due to the extended ${\pi}$-conjugation. The fluorescence quantum yields were measured as very small. Even though intersystem crossing rates were expected to increase due to the increment of spin orbital coupling, the triplet quantum yields were measured as less than 0.15. Such characteristics can be ascribed to the more enhanced internal conversion rates compared with the intersystem crossing rates. Furthermore, the triplet state lifetimes were shortened to -1.0 ${\mu}s$ as expected. Therefore, the singlet oxygen quantum yields were estimated to be near zero due to the fast triplet state decay rates and the inefficient energy transfer to the oxygen molecule as well as the low triplet quantum yields. The low efficiencies of energy transfer to the oxygen molecule can be attributed to the lower oxidation potential and/or the energetically low lying triplet state. Such photophysical factors should be carefully evaluated as potential photosensitizers that have extended ${\pi}$-conjugation and heavy core atoms synthesized for red-shifted absorption and high triplet state quantum yields.

• Bulletin of the Korean Chemical Society
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• 제24권11호
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• pp.1671-1674
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• 2003

The effects of amine donors ($a:NH_2,\;b:NMe_2,\;c:NMePh,\;d:NPh_2$) and conjugation length on the molecular hyperpolarizabilities of a series of dipolar molecules have been theoretically investigated by using CPHF/6-31G method. The first hyperpolarizabilities (${\beta}$) of p-nitrobenzene derivatives increase with the donor in the order, $NH_2\;<\;NMe_2\;<\;NMePh\;<\;NPh_2$, whereas slightly different order is observed in more conjugated derivatives, i.e., $NH_2\;<\;NPh_2\;<\;NMe_2\;<\;NMePh$. The result has been attributed to the extent of charge transfer and torsion angle. Moreover, the results show that "non-traditional" ${\pi}$-conjugation effect exists in small compounds and decreases as the conjugation length between donor and acceptor increases.

• Bulletin of the Korean Chemical Society
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• 제31권3호
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• pp.577-581
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• 2010

Spiro[fluorene-9,4'-[4H]indeno[1,2-b]furan] was synthesized, and its $\pi$-conjugation was efficiently elongated using palladium-catalyzed C-H arylation of a furan moiety. The resulting $\pi$-conjugated compounds showed intense fluorescence and extremely high thermal stability.

• Journal of applied mathematics & informatics
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• 제4권1호
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• pp.285-297
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• 1997

We will study the generalization of theorems on the pe-riodic locally - solvable FC-groups to the theorems on the periodic locally-solvable CC-groups. The main theorem is the Theorem A. For the proof the inverse limit of inverse system and topological ap-proch developed by Dixon is useful.

• Bulletin of the Korean Chemical Society
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• 제34권7호
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• pp.2148-2154
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• 2013

Three push-pull organic semiconductors, TPA-$Th_3$-MMN (1), TPA-ThTT-MMN (2), and TPA-ThDTT-MMN (3), comprising a triphenylamine donor and a methylene malononitrile acceptor linked by various ${\pi}$-conjugated thiophene units were synthesized, and the effects of the ${\pi}$-conjugated bridging unit on the photovoltaic characteristics of solution-processed small-molecule organic solar cells based on these semiconductors were investigated. Planar bridging units with extended ${\pi}$-conjugation effectively facilitated intermolecular ${\pi}-{\pi}$ packing interactions in the solid state, resulting in enhanced $J_{sc}$ values of the SMOSCs fabricated with bulk heterojunction films.