• Bulletin of the Korean Chemical Society
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• 제26권10호
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• pp.1505-1511
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• 2005

The excitation energy transfer process occurring in energy donor-acceptor linked porphyrin array system is theoretically simulated using the on-the-fly filtered propagator path integral method. The compound consists of an energy donating meso-meso linked Zn(II) porphyrin array and an energy accepting 5,15-bisphenylethynylated Zn(II) porphyrin, in which the donor array and the acceptor are linked via a 1,4-phenylene spacer. Real-time path integral simulations provide time-evolution of the site population and the excitation energy transfer rate constants are determined. Simulations and experiments show an excellent agreement indicating that the path integration is a useful tool to investigate the energy transfer dynamics in molecular assemblies.

• Bulletin of the Korean Chemical Society
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• 제28권1호
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• pp.33-40
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• 2007

We have designed and synthesized three Zn(II)-porphyrin derivatives, such as Zn(II) porphyrin ([G-0]Zn-P1) and aryl ether-typed dendron substituted Zn(II)-porphyrin derivatives ([G-1]Zn-P1 and [G-1]Zn-P-CN1). Their chemical structures were characterized by 1H-NMR, FT-IR, UV-vis absorption, EI-mass, and MALDI-TOF mass spectroscopies. Their electrochemical properties were studied by cyclic voltammetry measurement. These Zn(II)-porphyrin derivatives have been used to fabricate dye-sensitized solar cells (DSSCs) based on solid polymeric electrolytes as dye sensitizers and their device performances were evaluated by comparing with that of a standard Ru(II) complex dye. [G-1]Zn-P-CN1 showed the enhanced power conversion efficiency than those of other porphyrin derivatives, as expected. Short-circuit photocurrent density (Jsc), open-circuit voltage (Voc), fill factor (FF), and power conversion efficiency (η) of solid-typed DSSC for [G-1]Zn-P-CN1 were evaluated to be Jsc = 11.67 mA/cm2, Voc = 0.51 V, FF = 0.46, and η = 2.76%, respectively.

• Bulletin of the Korean Chemical Society
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• 제23권2호
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• pp.271-276
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• 2002

The energy relaxation dynamics of the lowest excited singlet and triplet states of the Zn(II)porphyrin monomer and its directly linked arrays were comparatively investigated with increasing the number of porphyrin moieties. While the fluorescence decay rates and quantum yields of the porphyrin arrays increased with the increase of porphyrin units, their triplet-triplet (T-T) absorption spectra and decay times remained almost the same. The difference in the trends of energy relaxation dynamics between the excited singlet and triplet states has been discussed in view of the electronic orbital configurations.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2002년도 하계학술대회 논문집 Vol.3 No.2
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• pp.752-755
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• 2002

Since Metallo-Porphyrin (MP) is very interesting compound due to its unique electronic and redox properties and it is also chemically and thermally stable, MP has been studied for potential memory and switching devices. In this study, thin films of 5,10,15,20 - Tetrakis - Octadecyloxymethylphenyl - Porphyrin - Zn(II) (Zn-TPP) were prepared by the Langmuir-Blodgett (LB) method and characterized by using UV/vis absorption spectroscopy and cyclic voltammetry. It was found that the proper transfer surface pressure for film deposition was 25 mN/m and the limiting area per molecule was $135{\AA}^2$/molecule. The current-voltage (I-V) characteristics of these films were investigated.

• KIEE International Transactions on Electrophysics and Applications
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• 제11C권3호
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• pp.58-62
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• 2001

Since Metallo-Porphyrin (MP) is very interesting compound due to its unique electronic and redox properties and it is also chemically and thermally stable, MP has been studied for potential memory and switching devices. In this study, thin films of 5,10,15,20-Tetrakis-Octadecyloxymethylphenyl-Porphyrin-Zn(II) were prepared by the Langmuir-Blodgett (LB) method and characterized by using UV/vis absorption spectroscopy and cyclic voltammetry. It was found that the proper transfer surface pressure for film deposition was 25 mN/m and the limiting area per molecule was 135 ${\AA}^2$/molecule. The current-voltage (I-V) characteristics of these films were investigated. Further details on the electrical properties of Porphyrin-Zn(II) derivative films will be discussed.

• 대한화학회지
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• 제35권5호
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• pp.512-519
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• 1991

유기용매$(CH_2Cl_2,\;C_6H_6,\;CH_3NO_2,\;(CH_3)_2CO,\;CHCl_3,\;DMF,\;DMSO)$에서 Zn(II)-, Cu(II)- 및 Ni(II)-tetrakis(o-chlorophenyl)porphyrin(o-ClTPP)과 Zn(II)-, Cu(II)- 및 Ni(II)-tetraphenylporphyrin(TPP) 착물과 질소원자를 포함한 염기성 리간드(pyridine, imidazole, 1-methylimidazole 및 2,6-lutidine)간의 결합 반응성을 이온강도 0.01M에서 연구하였다. metalloporphyrin과 염기성 리간드간의 평형상수는 온도범위 15 ~ 35${\circ}C$에서 분광광도법을 이용하여 결정하였으며, 이 때 M(II)-TPP에서 관찰된 평형상수는 입체적 장애가 더 큰 M(II)-(o-Cl)TPP에서 보다 큰 값을 나타내었다. M(II)-TPP에서 logK값은 염기성 리간드의 pKa값이 커질수록 증가하였지만 입체적장애를 받는 M(II)-(o-Cl)TPP에서 logK는 리간드의 $pK_a$값에 비례하지 않았다. 열역학적 파라미터 분석결과 M(o-Cl)TPP의 안정도는 거의 반응엔트로피에 의존하였으나, M(II)-TPPL의 안정도는 반응엔탈피와 반응엔트로피에 거의 비슷한 영향을 나타내었다. metalloporphyrin에 대한 용매의 배위능을 DMF, DMSO, $CHCl_3,\;(CH_3)_2CO$에서 측정하였고, 이들 결과로부터 평형상수에 대한 용매효과를 논의하였다.

• Bulletin of the Korean Chemical Society
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• 제24권8호
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• pp.1075-1080
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• 2003

We have investigated femtosecond coherent vibrational motions of Zn(II)-5,15-diphenylporphyrin in toluene using chirp-controlled ultrashort pulses. The oscillatory features superimposed on the temporal profiles of the pump-probe transient absorption signal are affected by the chirping and energy of excitation pulses. Using chirp- and excitation energy-controlled femtosecond pulses, we are able to obtain information on the structural changes between the electronic ground and excited states based on a comparative analysis of the Fouriertransformed frequency-domain spectra retrieved from the oscillatory components with the ground state resonance Raman spectra and normal mode calculations.

• 대한화학회지
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• 제35권5호
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• pp.569-574
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• 1991

pyrrole과 benzaldehyde 및 그 유도체로부터 meso-tetraphenylporphyrin(TPP)과 그 유도체 다섯가지를 합성한 후 이를 Co(II), Cu(II), Zn(II)의 염화물과 반응시켜 각각의 metalloporphyrin 착화합물을 만들고, 이 중 meso-tetra(p-aminophenyl)porphyrin(TNPP)을 다공성 polystyrene 수지와 반응시킨 후 여기에 Cu(II)의 염화물을 작용시켜 고분자결합 metalloporphyrin 착화합물 : Cu(Res-NH-TPP-$NH_2$)을 만들었다. 합성한 porthyrin 화합물들은 가시광선, 적외선 및 전자스핀공명 스펙트럼으로 확인하였고, 금속함량은 원자흡광 분광광도법으로 측정하였다. 합성한 porphyrin 화합물을 benzoquinone 광환원반응에 촉매로 이용한 결과, 일반적으로 유리 porphyrin보다 metalloporphyrin이, metalloporphyrin 중에는 Cu-TNPP의 촉매효과가 높았으며, 이에 고분자를 결합시키는 경우 효과가 더욱 향상됨을 알 수 있었다.

• 분석과학
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• 제8권4호
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• pp.511-517
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• 1995

A cationic water soluble porphyrin (5,10,15,20-tetrakis (l-methyl-pyridinium-4-yl)porphyrin, $H_2tmpyp^{4+}$) and its metalloporphyrins (MP) were easily extracted into acetonitrile separated by addition of sodium chloride ($4mol\;dm^{-3}$) in the presence of sodium perchlorate, where M denotes $Zn^{2+}$, $Cu^{2+}$, $Co^{3+}$, $Fe^{3+}$, and $Mn^{3+}$ and $P^{2-}$ is porphyrinate ion. The extracted ion-pair complexes were completely dissociated to $[MP(ClO_4)_3]^+$, and $[MP(ClO_4)_2]^{2+}$. The extraction and the dissociation constants were determined by taking into account of the partition constant of sodium perchlorate ($K_D=1.82{\pm}0.01$). The chemical properties of the separated acetonitrile phase as $E_{T(30)}$ and $D_{II,I}$ were determined and compared with other water miscible solvents (acetone, actonitrile, 1,4-dioxane, tetrahydrofuran, 1-propanol and 2-propanol). Furthermore, a sensitive and selective method was proposed for the determination of a subnanogram amount of copper(II) in natural water samples by using the present salting-out method and the porphyrins.

• Bulletin of the Korean Chemical Society
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• 제29권1호
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• pp.197-201
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• 2008

Conformational heterogeneity of directly linked multiporphyrin arrays with larger molecular length retards their utilities in practical applications such as two-photon absorption and molecular photonic wire. In this regard, here we adopted a way to overcome the conformational heterogeneity through hydrogen bonding by selective binding of meso aryl substituents of porphyrins (host) with urea (guest) to form helical structure. Using steady-state and time-resolved spectroscopy, we observed the enhanced fluorescence quantum yield by ~1.8 to 2.4 times, enhanced anisotropy values and the disappearance of fast fluorescence decay component in the host-guest helical forms. In addition, the enhanced nonlinear optical responses of helical arrays infer the extended inter-porphyrin electronic coupling due to a significant change in dihedral angle between the neighboring porphyrin moieties. The current host-guest strategy will provide a guideline to improve the structural homogeneity of the photonic wire.