• Bulletin of the Korean Chemical Society
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• v.26 no.10
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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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• v.28 no.1
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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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• v.23 no.2
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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.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.07b
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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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• v.11C no.3
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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.

• Journal of the Korean Chemical Society
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• v.35 no.5
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• pp.512-519
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• 1991

The axial ligations of nitrogenous bases (pyridine, imidazole, 1-methylimidazole and 2,6-lutidine) to Zn(II)-, Cu(II)-, and Ni(II)-tetrakis(o-chlorophenyl)porphyrin(o-ClTPP), and -tetraphenylporphyrin (TPP) were investigated in organic solvents $(CH_2Cl_2,\;C_6H_6,\;CH_3NO_2,\;(CH_3)_2CO,\;CHCl_3,\;DMF\;and\;DMSO)$ and at 0.01M of ionic strength. The equilibrium constants for the ligation reactions of methalloporphyrins were determined using spectrophotometric method at 15∼35${\circ}C$. In case of M(II)-TPP the equilibrium constants K were considerably larger than those of M(II)-(o-Cl)TPP, depending on steric effect of the porphyrin. The linear relationships between logK of the axial ligation and $pK_a$ of nitrogenous base were shown in M(II)-TPP, but not in M(II)-(o-Cl)TPP. The stabilities of MTPP(L) were controlled by the reation enthalpy and entropy, while those of M(o-Cl)TPP almost by the reaction entropy. The coordinating power of solvent to the methalloporphyrin were also studied in $CHCl_3,\;(CH_3)_2CO$, DMF and DMSO. From those results the solvent effects on the equilibrium constants were discussed.

• Bulletin of the Korean Chemical Society
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• v.24 no.8
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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.

• Journal of the Korean Chemical Society
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• v.35 no.5
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• pp.569-574
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• 1991

Six free base porphyrins were synthesized by reacting pyrrole with benzaldehyde or its derivatives and then reacted with metal chlorides to prepare corresponding metal complexes. In addition, polymer-bonded porphyrins were synthesized by treating chloromethylated styrene-divinyl benzene (1%) copolymer beads with meso-tetra (p-aminophenyl)porphyrin (TNPP) solution and then treated with cupric chloride to obtain Cu(Res-NH-TPP-$NH_2$). The porphyrin compounds were characterized by visible, inffrared and electron spin resonance spectral analyses. The metal contents of metalloporphyrins were determined by atomic adsorption spectrophotometry. The synthesized porphyrin compounds were subsequently examined for their catalytic strength and found the activity to increase in the following order: free base porphyrins; metalloporphyrins; polymer-bonded metalloporphyrin. Among metalloporphyrins, Cu-TNPP showed the greatest catalytic power.

• Analytical Science and Technology
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• v.8 no.4
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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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• v.29 no.1
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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.