• Title/Summary/Keyword: $\pi$-Acceptors

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Physical Properties of Octahedral Iron (Ⅱ) Complexes of Vicinal-Dioximes (팔면체형 철 (Ⅱ) Vicinal-디옥심 착물의 물리적 성질)

  • Chong-Shik Chin;L. Vaska
    • Journal of the Korean Chemical Society
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    • v.24 no.5
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    • pp.380-392
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    • 1980
  • Six coordinate low spin iron(Ⅱ) complexes of vicinal-dioximes, [Fe$(DH)_2B_2$] and [Fe$(DH)_2$B(CO)]($(DH)_2$=$(CHDH)_2$(bis(1,2-cyclohexadinedioximato) bivalent anion), $(DPGH)_2$-(bis(diphenylglyoximato) bivalent anion), $(F{\alpha}DH)_2(bis(furil-{\alpha}-dioximato)$ bivalent anion); B = monodentate neutral nitrogen base), have been prepared and their physical properties have been investigated with respect to the effects of the equatorial ligands, $(DH)_2$. The order of ${\pi}$-acceptor CO stretching frequency for [Fe$(DH)_2$B(CO)] is $(F{\alpha}DH)_2$ > $(DPGH)_2$> $(CHDH)_2$, while non-${\pi}$-acceptor $NH_3$ stretching frequencies for [Fe$(DH)_2(NH_3)_2$] show the opposite order to that of CO, i.e., $(CHDH)_2$ > $(DPGH)_2$ > $(F{\alpha}DH)_2$. These infrared spectral data together with Fe-N (oxime) and Fe-N (oxime) and Fe-N (B) stretching frequency data suggest that the nitrogen atoms of $(CHDH)_2$ are more basic and poorer ${\pi}$-acceptors than the corresponding nitrogen atoms of $(DPGH)_2$ and $(F{\alpha}DH)_2$, respectively. It has been found from the electronic spectral data of [Fe$(DH)_2$] and [Fe$(DH)_2$B(CO)] that the energy of the charge transfer band from iron(Ⅱ) to $(DH)_2$ increases as the basicity of $(DH)_2$ increases.

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Geometrical Characteristics and Atomic Charge Variations of Pd(II) Complexes [Pd(L)Cl2] with an Axial (Pd·O) Interaction

  • Park, Jong-Keun;Cho, Yong-Guk;Lee, Shim-Sung;Kim, Bong-Gon
    • Bulletin of the Korean Chemical Society
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    • v.25 no.1
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    • pp.85-89
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    • 2004
  • Geometrical structures of [Pd(L)$Cl_2$] with oxathia macrocycles have been calculated using ab initio secondorder Moller-Plesset (MP2) and Density Functional Theory (DFT) methods with triple zeta plus polarization (TZP) basis set level. In optimized Pd(L)$Cl_2$ complexes, Pd(II) locates at the center surrounded by a square planar array of two sulfurs on an oxathia macrocycle and two chlorides. The endo-Pd(II) complexes with an axial (Pd${\cdots}$O) interaction are more stable than the exo-Pd(II) complexes without the interaction. In the endo-Pd(II) complexes, the atomic charge of the oxygen atom moves to Pd(II) via the axial ($Pd{\cdots}$O) interaction and then, the charge transfer from Pd(II) to the S-atoms occurs stepwise via ${\pi}$-acceptors of the empty d-orbitals.

Photochemical Index Analysis on Different Shading Level of Garden Plants (정원 식물의 차광 조건별 광화학적 생리지표 해석)

  • Kang, Hong Gyu;Kim, Tae Seong;Park, So Hyun;Kim, Tae Wan;Yoo, Sung Yung
    • Korean Journal of Environmental Biology
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    • v.34 no.4
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    • pp.264-271
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    • 2016
  • The objective of this study was to determine the growth and light utilization efficiency of garden plants in shade area through chlorophyll fluorescence reaction analysis. Ten garden plants was grown for 75 days under 50% and 80% shading conditions. Under shading, $ET2_O/RC$, the fluorescence parameter related to electron-transport in photosystem II, was effectively enhanced. However, the electron transport flux until PSI acceptors per reaction center ($RE1_O/RC$) was reduced. These changes in photochemical parameters evoked a decrease in performance index (PI) and driving force (DF) of electron transport flux. In addition, some photochemical parameters such as $F_V$, $FV/F_O$, $RE1_O/RC$, $ET2_O/RC$, $PI_{TOTAL\;ABS}$, and $DF_{TOTAL\;ABS}$ were found to be important for shade tolerance. Three species (Pachysandra terminalis Siebold & Zucc, Physostegia virginiana L., and Carex maculata Bott) were found to be shade tolerant. Based on these results, shading factor index (SFI) deduced from photochemical parameters is useful for evaluating of shading stress of garden plants.

The Physicochemical Properties on the Charge Transfer Complexes under High Pressure (고압하의 전하이동착물에 대한 물성론적 연구-사염화탄소 용액내에서 헥사메틸벤젠과 여러 전자받게들간의 전하이동착물 생성에 대한 압력과 온도의 영향)

  • Kwun Oh Cheun;Kim Myong Ja;Kim Se Kyung
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.335-342
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    • 1991
  • The effect of pressure and temperature on the stabilities of the charge transfer complexes of 1,3,5-trinitrobenzene, tetrachloro-p-benzoquinone and tetracyanoethylene with hexamethylbenzene in carbon tetrachloride has been investigated by spectrophotometric measurements. The equilibrium constants for the formation of the complexes were obtained at various temperature and pressure, and thermodynamic parameters for the formation of the charge transfer complexes are calculated from these values. The relative stabilities of charge transfer complexes with hexamethylbenzene increase in the order; 1,3,5-trinitrobenzene < tetrachloro-p-benzoquinone < tetracyanoethylene. This may be regarded as an order of relative acidity of these compounds in complexation with hexamethylbenzene and is explained in terms of the negative inductive effect of the ${\pi}$ acceptors. The red-shift at higher pressure, the blue-shift at higher temperature and the relation between pressure and oscillator strength are discussed on the basis of thermodynamic functions.

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