• Bulletin of the Korean Chemical Society
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• v.25 no.4
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• pp.443-444
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• 2004

• Bulletin of the Korean Chemical Society
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• v.26 no.2
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• pp.201-214
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• 2005

We have designed and developed novel luminescent lanthanide complexes for advanced photonics applications. Lanthanide(III) ions (Ln$^{3+}$) were encapsulated by the luminescent ligands such as metalloporphyrins and naphthalenes. The energy levels of the luminescent ligands were tailored to maintain the effective energy transfer process from luminescent ligands to Ln$^{3+}$ ions for getting a higher optical amplification gain. Also, key parameters for emission enhancement and efficient energy transfer pathways for the sensitization of Ln$^{3+}$ ions by luminescent ligands were investigated. Furthermore, to enhance the optophysical properties of novel luminescent Ln$^{3+}$ complexes, aryl ether-functionalized dendrons as photon antennas have been incorporated into luminescent Ln$^{3+}$ complexes, yielding novel Ln(III)-cored dendrimer complex. The novel Ln(III)-cored dendrimer complex has much higher PL intensity than the corresponding simple complex, due to the efficient site-isolation effect. In this article, we will deal with recent progress in the synthesis and photophysical studies of inert and stable luminescent Ln$^{3+}$ complexes for advanced photonics applications. Also, our review will include the exploratory investigation of the key parameters for emission enhancement and the effective energy transfer pathways from luminescent ligands to Ln$^{3+}$ ions with Ln(III)-chelated prototype complexes.

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1729-1730
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• 2006

• Rapid Communication in Photoscience
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• v.1 no.1
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• pp.1-9
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• 2012

Luminescent lanthanide complexes have been overviewed for advanced photonics applications. Lanthanide(III) ions ($Ln^{3+}$) were encapsulated by the luminescent ligands such as metalloporphyrins, naphthalenes, anthracene, push-pull diketone derivatives and boron dipyrromethene(bodipy). The energy levels of the luminescent ligands were tailored to maintain the effective energy transfer process from luminescent ligands to $Ln^{3+}$ ions for getting a higher optical amplification gain. Also, key parameters for emission enhancement and efficient energy transfer pathways for the sensitization of $Ln^{3+}$ ions by luminescent ligands were investigated. Furthermore, to enhance the optophysical properties of novel luminescent $Ln^{3+}$ complexes, aryl ether-functionalized dendrons as photon antennas have been incorporated into luminescent $Ln^{3+}$ complexes, yielding novel $Ln^{3+}$-cored dendrimer complex such as metalloporphyrins, naphthalenes, and anthracenes bearing the Fr$\acute{e}$chet aryl-ether dendrons, namely, ($Er^{3+}-[Gn-Pt-Por]_3$ (terpy), $Er^{3+}-[Gn-Naph]_3$(terpy) and $Er^{3+}-[Gn-An]_3$(terpy)). These complexs showed much stronger near-IR emission bands at 1530 nm, originated from the 4f-4f electronic transition of the first excited state ($^4I_{13/2}$) to the ground state ($^4I_{15/2}$) of the partially filled 4f shell. A significant decrease in the fluorescence of metalloporphyrins, naphthalenes and anthracene ligand were accompanied by a strong increase in the near IR emission of the $Ln^{3+}$ ions. The near IR emission intensities of $Ln^{3+}$ ions in the lanthanide(III)-encapsulated dendrimer complexes were dramatically enhanced with increasing the generation number (n) of dendrons, due to the site-isolation and the light-harvesting(LH) effects. Furthermore, it was first attempted to distinguish between the site-isolation and the light-harvesting effects in the present complexes. In this review, synthesis and photophysical studies of inert and stable luminescent $Ln^{3+}$ complexes will be dealt for the advanced photonics applications. Also, the review will include the exploratory investigation of the key parameters for emission enhancement and the effective energy transfer pathways from luminescent ligands to $Ln^{3+}$ ions with $Ln^{3+}$-chelated prototype complexes.

• Journal of Photoscience
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• v.10 no.1
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• pp.175-180
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• 2003

Zeolite, Nafion membranes and vesicles were used as microreactors to control the pathway of photosensitized oxidation of alkenes and remarkable selectivity was achieved.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1181-1185
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• 1999

The reaction of FeC5H5+ ion with ferrocene molecule is investigated using FT-ICR mass spectrometry. FeC5H5+ ions are generated by dissociative ionization of ferrocenes using an electron beam. The reaction gives rise to the formation of the adduct ion, Fe2(C5H5)3+, in competition with charge transfer reaction leading to the formation of ferrocene molecular ion, Fe(C5H5)2+·. The branching ratio of the adduct ion increases as the internal energy of the reactant ion decreases and correspondingly the branching ratio for the charge transfer reaction product decreases. The observed rate of the addition reaction channel is slower than that of the charge transfer reaction. The observation of the stable adduct ions in the low-pressure ICR cell is attributed to the radiative cooling of the activated ion-molecule complex. The mechanism of the reaction is presented to account for the observed experimental results.

• Journal of the Korean Chemical Society
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• v.67 no.6
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• pp.407-414
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• 2023

The present study uses quasi-classical trajectory procedures to examine the vibrational relaxation and dissociation of the methyl and ring C-H bonds in excited methylpyrazine (MP) during collision with either N₂ or O₂. The energy-loss (-ΔE) of the excited MP is calculated as the total vibrational energy (E_T) of MP is increased in the range of 5,000 to 40,000cm^-1. The results indicate that the collision-induced vibrational relaxation of MP is not large, increasing gradually with increasing E_T between 5,000 and 30,000 cm^-1, but then decreasing with the further increase in E_T. In both N₂ and O₂ collisions, the vibrational relaxation of MP occurs mainly via the vibration-to-translation (V→T) and vibration-to-vibration (V→V) energy transfer pathways, while the vibration-to-rotation (V→R) energy transfer pathway is negligible. In both collision systems, the V→T transfer shows a similar pattern and amount of energy loss in the ET range of 5,000 to 40,000cm^-1, whereas the pattern and amount of energy transfer via the V→V pathway differs significantly between two collision systems. The collision-induced dissociation of the C-H_methyl or C-H_ring bond occurs when highly excited MP (65,000-72,000 cm^-1) interacts with the ground-state N₂ or O₂. Here, the dissociation probability is low (10^-4-10^-1), but increases exponentially with increasing vibrational excitation. This can be interpreted as the intermolecular interaction below E_T = 71,000 cm^-1. By contrast, the bond dissociation above E_T = 71,000 cm^-1 is due to the intramolecular energy flow between the excited C-H bonds. The probability of C-H_methyl dissociation is higher than that of C-H_ring dissociation.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3641-3648
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• 2013

Energy transfer and bond dissociation of $C-H_{methyl}$ and $C-H_{ring}$ in excited toluene in the collision with $H_2$ and $D_2$ have been studied by use of classical trajectory procedures at 300 K. Energy lost by the vibrationally excited toluene to the ground-state $H_2/D_2$ is not large, but the amount increases with increasing vibrational excitation from 5000 and $40,000cm^{-1}$. The principal energy transfer pathway is vibration to translation (V-T) in both systems. The vibration to vibration (V-V) step is important in toluene + $D_2$, but plays a minor role in toluene + $H_2$. When the incident molecule is also vibrationally excited, toluene loses energy to $D_2$, whereas it gains energy from $H_2$ instead. The overall extent of energy loss is greater in toluene + $D_2$ than that in toluene + $H_2$. The different efficiency of the energy transfer pathways in two collisions is mainly due to the near-resonant condition between $D_2$ and C-H vibrations. Collision-induced dissociation of $C-H_{methyl}$ and $C-H_{ring}$ bonds occurs when highly excited toluene ($55,000-70,400cm^{-1}$) interacts with the ground-state $H_2/D_2$. Dissociation probabilities are low ($10^{-5}{\sim}10^{-2}$) but increase exponentially with rising vibrational excitation. Intramolecular energy flow between the excited C-H bonds occurring on a subpicosecond timescale is responsible for the bond dissociation.

• Bulletin of the Korean Chemical Society
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• v.1 no.2
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• pp.45-49
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• 1980

During the homolytic reactions of $CCl_4$ or $Cl_3CBr with ${\beta}-halo^1$-styrenes,$\beta$-haloradicals are key intermediates. They are to be stabilized via three pathways; $\beta$-cleavage, halogen transfer and telomerization. The three reaction paths are delicately controlled by the energetics of their formation and stabilization. When the formation of a $\beta$-haloradical is accompanied by considerable excess of energy from an exothermic reaction, $\beta$ -cleavage is often dominant over the halogen transfer. On the other hand, if the radical forms via a reversible reaction, two processes become competitive. $\beta$-Eliminated bromine atoms from ${\beta}$ -bromoradicals generate $Br_2$ via $Cl_3CBr + {\cdot}Br {\leftrightarrow} Br_2 + {CCl_3}{\cdot}{Br_2}$ may act as a better scavenger than Cl3CBr for the ${\beta}$-bromoradicals. Different reactivities of chlorine, bromine and trichloromethyl radicals towards olefinic pi-bond are clarified in terms of the beat content of the addition reactions.

• Macromolecular Research
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• v.16 no.3
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• pp.224-230
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• 2008

This study examined the photoemission behaviors of isolated chains of poly[2-methoxy, 5-(2'-ethylhexyloxy)-1,4-phenylenevinylene](MEH-PPV) dispersed in various solvents including dichloromethane, chloroform and tetrahydrofuran(THF). A change in polymer-solvent interactions in these solutions caused the MEH-PPV chains to adopt different local conformations, which in turn affected their radiative de-excitation pathways. For the polymer in dichloromethane and chloroform, in which the conjugated chains are relatively extended, photoemission occurs mostly at the long chromophores with lowest HOMO-LUMO energy gap. Their emission spectra showed a main peak at ${\sim}560\;nm$. Dual photoemission of high- and low-energy chromophores was observed when the conjugated chains were forced to partially collapse in a poor solvent THF. Novel high-energy peaks and a typical low-energy peak were detected at ${\sim}414\;nm$ and ${\sim}554\;nm$, respectively. The observation of the high-energy peaks indicates significant suppression of the intrachain energy transfer process, which was attributed to the increase in conformational disorder in the partially collapsed coils. An analysis of the excitation spectra suggests that the high-energy peaks belong to short chromophores constituting of one or two repeat units. This study systematically investigated the effects of polymer concentration, temperature and single bond defects along the backbone on the photoemission of the high-energy chromophores.