• 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.32 no.8
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• pp.2743-2750
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• 2011

Lanthanide(III)-cored complex as a wavelength conversion material has been successfully designed and synthesized for highly efficient dye-sensitized solar cells, for the first time, since light with a short wavelength has not been effectively used for generating electric power owing to the limited absorption of these DSSCs in the UV region. A black dye (BD) was chosen and used as a sensitizer, because BD has a relatively weak light absorption at shorter wavelengths. The overall conversion efficiency of the BD/WCM device was remarkably increased, even with the relatively small amount of WCM added to the device. The enhancement in $V_{oc}$ by WCM, like DCA, could be correlated with the suppression of electron recombination between the injected electrons and $I_3{^-}$ ions. Furthermore, the short-circuit current density was significantly increased by WCM with a strong UV light-harvesting effect. The energy transfer from the Eu(III)-cored complex to the $TiO_2$ film occurred via the dye, so the number of electrons injected into the $TiO_2$ surface increased, i.e., the short-circuit current density was increased. As a result, BD/WCM-sensitized solar cells exhibit superior device performance with the enhanced conversion efficiency by a factor of 1.22 under AM 1.5 sunlight: The photovoltaic performance of the BD/WCM-based DSSC exhibited remarkably high values, $J_{sc}$ of 17.72 mA/$cm^2$, $V_{oc}$ of 720 mV, and a conversion efficiency of 9.28% at 100 mW $cm^{-2}$, compared to a standard DSSC with $J_{sc}$ of 15.53 mA/$cm^2$, $V_{oc}$ of 689 mV, and a conversion efficiency of 7.58% at 100 mW $cm^{-2}$. Therefore, the Eu(III)-cored complex is a promising candidate as a new wavelength conversion coadsorbent for highly efficient dye-sensitized solar cells to improve UV light harvesting through energy transfer processes. The abstract should be a single paragraph which summaries the content of the article.

• Bulletin of the Korean Chemical Society
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• v.28 no.8
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• pp.1249-1255
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• 2007

We have investigated the photophysical properties of dansyl-N-methylaminobenzoic acid (DABAH) as a ligand and its lanthanide (Ln3+)-cored complexes (Ln3+-(DABA)3(terpy)) in order to determine the main energy transfer pathway for sensitized near infrared emission of Ln3+ ions (Ln3+ = Nd3+ and Er3+) in Ln3+- (DABA)3(terpy). The fluorescence spectrum of DABAH shows a large Stokes shift with increasing solvent polarity. This large Stokes shift might be due to the formation of a twisted intramolecular charge transfer (TICT) state, as demonstrated by the large dipole moment in the excited state. It is in good agreement with the result that the phosphorescence even in the Gd3+-cored complex based on the DABAH ligand was not observed, maybe due to the highly forbidden character of the S1 → T1 transition in the DABAH ligand. A short decay component (ca. 1 ns) was observed in Er3+-(DABA)3(terpy) whereas the fluorescence lifetimes of DABAH and its Gd3+-(DABA)3(terpy) are observed about ~10 ns. The short component could be originated from the energy transfer process between the ligand and the Ln3+ ion. Based on the fluorescence of DABAH its Ln3+- (DABA)3(terpy), the sensitization of Ln3+ luminescence in the Ln3+-(DABA)3(terpy) takes place by the energy transfer via the TICT state of DABAH in the excited singlet state rather than via the excited triplet state.

• 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.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1553-1558
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• 2009

A series of Eu(III) complexes with various neutral ligands (2,2’:6’,2"-terpyridine (T), diglyme (D), 1N-(2-dimethylamino) ethyl)-1N, 2N, 2N-trimethylethane-1,2-diamine (PT), di-(2-picolyl)-amine derivative (HT), and multidentate terpyridine derivative (DT)) were synthesized to investigate the effect of coordination environment on the sensitized luminescence of Eu(III) complexes. The nine coordination sites of the $Eu^{3+}$ ion are occupied by three bidentate carboxylate moieties and one neutral ligand. The highest emission intensity is obtained for $Eu^{3+}$- $[NA]_3$ (PT), due to the difference in energy transfer efficiency and symmetry of the first coordination sphere of $Eu^{3+}$ ion. But, the lowest emission intensity is obtained for $Eu^{3+}$-$[NA]_3$(T). Terpyridine may not play an important role antenna for photosensitizing $Eu^{3+}$ ion. It could be attributed to the weak spectral overlap integral J value between its phosphorescence band and $Eu^{3+}$ion absorption band. Therefore, different coordination environment of $Ln^{3+}$ ion play an important role in providing sensitization of lanthanide ion emission.