• Macromolecular Research
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• v.17 no.9
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• pp.672-681
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• 2009

A series of inert and photo-stable Er(III)-encapsulated complexes based on ${\pi}$-extended dendritic anthracene ligands bearing G3-aryl-ether dendron ([G3-AnX]-$CO_2H$), which retain different ${\pi}$-bridging systems, such as single (X= S), double (X= D) and triple (X= T) bonds was designed and synthesized to establish the structure-property relationship. The near infrared emission intensities of Er(III)-encapsulated complexes were enhanced dramatically by increasing the ${\pi}$-conjugated extension of anthracene ligands. The time-resolved luminescence spectra show monoexponential decays with a lifetime of $2.0{\sim}2.4ms$ for $Er^{3+}$ ions in thin films, and calculated intrinsic quantum yields of $Er^{3+}$ ions are in the range of $0.025{\sim}0.03%$. As a result, all Er(III)-encapsulated dendrimer complexes exhibit the near IR emission with the following order: $Er^{3+}-[G3-AnD]_3$(terpy) > $Er^{3+}-[G3-AnS]_3$(terpy) ${\approx}$ $Er^{3+}-[G3-AnT]_3$(terpy), because $Er^{3+}-[G3-AnD]_3$(terpy) has a higher relatively spectral overlap J value and energy transfer efficiency. In addition, the lack of detectable phosphorescence and no significant spectral dependence of the ${\pi}$-extended anthracene moieties on the solvent polarity support energy transfer from their singlet state to the central $Er^{3+}$ ion taking place in $Er^{3+}-[G3-AnX]_3$(terpy).

• Macromolecular Research
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• v.12 no.1
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• pp.100-106
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• 2004

We have prepared the polymethylene-bridged, dinuciear, half-sandwich constrained geometry catalysts (CGC)［Zr(η$\^$5/:η$^1$-C$\_$9/H$\_$5/SiMe$_2$NCMe$_3$)］$_2$［(CH$_2$)$\_$n/］［n=6(9), n=12(10)］by treating 2 equivalents of ZrCl$_4$with the corresponding tetralithium salts of the ligands in toluene. $^1$H and $\^$13/C NMR spectra of the synthesized complexes provide firm evidence for the anticipated dinuciear structure. In $^1$H NMR spectra, two singlets representing the methyl group protons bonded at the Si atom of the CGC are present at 0.88 and 0.64 ppm, which are considerably downfield positions relative to the shifts of 0.02 and 0.05 ppm of the corresponding ligands. To investigate the catalytic behavior of the prepared dinuciear catalysts, we conducted copolymerizations of ethylene and styrene in the presence of MMAO. The prime observation is that the two dinuclear CGCs 9 and 10 are not efficient for copo-lymerization, which definitely distinguishes them from the corresponding titanium-based dinuclear CGC. These species are active catalysts, however, for ethylene homopolymerization; the activity of catalyst 10, which contains a 12-methylene bridge, is larger than that of 9 (6-methylene bridge), which indicates that the presence of the longer bridge between the two active sites contributes more effectively to facilitate the polymerization activity of the dinuciear CGC. The activities increase as the polymerization temperature increases from 40 to 70$^{\circ}C$. On the other hand, the molecular weights of the polyethylenes are reduced when the polymerization temperature is increased. We observe that dinuciear metallocenes having different-length bridges give different polymerization results, which reconfirms the significant role that the nature of the bridging ligand has in controlling the polymerization properties of dinuclear catalysts.

• Polymer(Korea)
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• v.24 no.2
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• pp.159-167
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• 2000

The polymethylene-bridged dinuclear half-titanocenes [(CH$_2$)$_{n}$(C$_{5}$ H$_4$)$_2$][TiCl$_3$]$_2$ (n=5(10), 7(11), 9(12)) have been synthesized by treating the distannylated derivatives of the ligands with two equivalents of TiCl$_4$ in toluene. All complexes are characterized by IR, $^1$H NMR, $^{13}$ C NMR and mass spectrometry. In order to examine the catalytic properties of the dinuclear complexes styrene polymerization has been conducted in the presence of MMAO. From the polymerization experiments it was found that ( i ) all the prepared complexes 10-12 produced syndiotactic polystyrenes, ( ii ) the complex 12 holding the longest bridging ligand exhibited the highest activity but produced a polymer having the smallest molecular weight among the polymethylene-bridged dinuclear half-titanocenes. This behavior was attributed to the influence of electron-donating caused by the polymethylene bridge between two active centers as well as the effect of steric congestion around metal center caused by the proximal distance between two active sites.s.

• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.633-643
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• 1989

The R$Rh_2(ap)_4$(2,2-trans) isomer (ap = 2-anilinopyridinate), which has two anilino nitrogens and two pyridyl nitrogens bound to each rhodium ion trans to their own kind, shows activation towards the one electron reduction of dioxygen at -0.40 V vs SCE. The ESR spectrum taken at 123 K proves the formation of a $[Rh_2(ap)_4(O_2)]$ ion with oxygen axially bound to one rhodium ion and the complex is at a RhⅡ2 oxidation state. The complex will form [$Rh_2(ap)_4(O_2)(CH_3CN)]^-$ in presence of $CH_3CN/CH_2Cl_2$ mixture without breaking the Rh-$O_2^-$ bond. When oxidized at -0.25 and 0.55 V, $[Rh_2(ap)_4(O_2)]$ will undergo two one electron oxidations to form $Rh_2(ap)_4(O_2)[Rh_2(ap)_4(O_2)]^+$. Both species have an axially bound superoxide ion but the former is at $Rh^{II}Rh^{III }$and the later at $Rh^{III}_2$ oxidation states. The ESR spetra and $CH_3CN$ addition study, on the other hand, show that the later complex is better described as $[Rh_{II}Rh^{III}(ap)_4(O_2)]^+$ with the odd electron localized on rhodium ion and the complex has an axially coordinated molecular oxygen. The electrochemical and ESR studies also show that the degree of dioxygen activation is a function of electrochemical redox potential.