• Bulletin of the Korean Chemical Society
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• 제28권11호
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• pp.1967-1972
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• 2007

Photophysical properties of a newly-synthesized porphyrin derivative, trans-bis(ferrocene carboxylato)- (5,10,15,20-tetraphenylporphyrinato)tin(IV) [Sn(TPP)(FcCOO)2] were investigated by means of steady-state and fs-time resolved laser spectroscopic techniques, and compared with those of a standard molecule, trans-dichloro( 5,10,15,20-tetraphenyl-porphrinato)tin(IV) [Sn(TPP)Cl2]. The fluorescence spectrum of Sn(TPP)- (FcCOO)2 was observed to exhibit dual emission bands originating from the S2-state and the S1-state, which was greatly quenched as compared to those of Sn(TPP)Cl2. The fs-time resolved fluorescence and transient absorption spectroscopic measurements revealed that the fluorescence quenching is due to formation of the long-lived charge transfer state by intramolecular electron transfer from ferrocene to the S2-excited SnTPP in addition to the enhanced non-radiative deactivation processes.

• 한국응용과학기술학회지
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• 제25권4호
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• pp.411-417
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• 2008

A group of new N,N-bis(5-acetylpyridin-2-yl)phenylamine derivatives was synthesized in good yield applying an optimized Buchwald-Hartwig amination protocol. The synthesized compounds showed UV absorption maxima in the range of 320-360 nm, and showed good luminescence at dilute concentrations in the blue region of the spectra (in the range of 480-497 nm). They showed also a bathochromic shift associating the increase in solvent polarity. The synthesized compounds could be investigated for use in OLEDs or as potential monomers for PLEDs.

• Bulletin of the Korean Chemical Society
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• 제16권3호
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• pp.202-204
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• 1995

The ultraviolet photochemistry of N,N'-bis(salicylidene)ethylenediamine copper(II), Cu(sal)2en, was investigated with low pressure mercury lamp. Redution of Cu(Ⅱ) and formation of Cl- were shown on 254 nm irradiation both for aerated and deaerated chlorinated hydrocarbon solvent such as CH2Cl2, chloroform, and 1,2-dichloroethane. Relatively long lived $({\tau}=100{\mu}sec)$ intermediate was detected by flash photolysis. Overall photo-process can be described as the formation of Cl- and new copper complex, product(1) by chlorohydrocarbon mediation, photoinduced reduction by abstraction of halogen from solvent, followed by redox induced substitution of axial ligand with chlorine. Product(1) is possibly Cu(III) chlorosalicylaldeimido complex and cyclic -CH2CH2- moiety is absent in the structure. 247nm band of Cu(sal)2en should contain ligand to metal charge transfer character.

• Bulletin of the Korean Chemical Society
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• 제24권4호
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• pp.446-452
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• 2003

Some new nanohybrid materials have been synthesized by intercalating the oxotitanium(IV) meso-tetrakis(4- sulfonatophenyl) porphyrin$(O=Ti^{(IV)} TSPP)$ into the Zn/Al layered double hydroxides (LDHs), and their structures and photophysical properties have been investigated by various laser spectroscopic techniques. According to the XRD pattern of the synthesized nanohybrid materials, the macrocycle plane of $O=Ti^{(IV)}$ TSPP are grafted perpendicular to the LDH layers. The $O=Ti^{(IV)}$ TSPP-intercalated LDH exhibits band broadening of the absorption spectrum and a blue shift of Q-band as compared to that observed in solution. Resonance Raman spectral measurements demonstrate that the positively charged LDHs give rise to a slight decrease of the electronic density of the porphyrin ring accompanying a small change of the electronic distribution of the $O=Ti^{(IV)}$ TSPP. Consequently the LDH environment affects the energies of the two highest occupied molecular orbitals (HOMOs) of the $O=Ti^{(IV)}$) TSPP, $a_{1u}$ and $a_{2u}$, producing a mixed orbital character. Being consistent with these electronic structural changes of $O=Ti^{(IV)}$ TSPP in LDH, both the fluorescence spectral change and the fsdiffuse reflectance transient measurements imply that the photoexcitation of the $O=Ti^{(IV)}$ TSPP intercalated into LDH undergoes fast relaxation to the O=Ti(IV) $TSPP^+-LDH^- $charge transfer (CT) state within a few picoseconds, followed by a photoinduced electron transfer between the O=Ti(IV) TSPP and LDHs with a rate constant greater than %1×10^{10}S^{-1}$. No evidence is found for back electron transfer. In conclusion, the $O=Ti^{(IV)}$ TSPP intercalated LDH seems to be a possible candidate for an artificial reaction center for an efficient solar energy conversion system.