• Korean Journal of Crystallography
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• v.16 no.2
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• pp.61-65
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• 2005

Despite a short history, the research on porous coordination polymers is gaining importance in inorganic chemistry thanks to facile synthesis, unambiguous characterization by X-ray diffraction and potentials as high-surface-area materials. Recently, gas sorption properties of various porous materials are under active investigations in order to know whether it is possible to store industrially important gases through physisorption, and porous coordination polymers are one of the most promising candidates for such a purpose. This article reviews two recent papers reporting a series of isomorphous frameworks based on Zn(II), dicarboxylate and diamine ligands and their gas sorption properties.

• Bulletin of the Korean Chemical Society
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• v.25 no.10
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• pp.1477-1483
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• 2004

We present the tandem mass spectrometry applications carried out to elucidate the coordination structure of Zn(II) bound lysine ternary complexes, $(Zn+Lys+Lys-H)^+$, which is a good model system to represent a simple (metallo)enzyme-substrate complex (ES). In particular, experimental efforts were focused on revealing the involvement of a lysine side chain ${\varepsilon}$-amino group in the coordination of $Zn^{2+}$ divalent ions. MS/MS fragmentation pattern showed that all the oxygen species within a complex fell off in the form of $H_2O$ in contrast to those of other ternary complexes containing amino acids with simple side chains (4-coordinate geometries, Figure 1a), suggesting that the lysine complexes have different coordination structures from the others. The participation of a lysine basic side chain in the coordination of Zn(II) was experimentally evidenced in MS/MS for $N{\varepsilon}$-Acetyl-L-Lys Zn(II) complexes with acetyl protection groups as well as in MS/MS for the ternary complexes with one $NH_3$ loss, $(Zn+Lys+Lys-NH_3-H)^+$. Detailed structures were predicted using ab initio calculations on $(Zn+Lys+Lys-H)^+$ isomers with 4-, 5-, and 6-coordinate structures. A zwitterionic 4-coordinate complex (Figure 7d) and a 5-coordinate structure with distorted bipyramidal geometry (Figure 7b) are found to be most plausible in terms of energy stability and compatibility with the experimental observations, respectively.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.636-640
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• 2012

We modify ZnO nanorods with Zn-porphyrin to obtain the improved characteristics of energy transfer, which is further investigated for the applicability to photovoltaic devices. A nitrogen heterocyclic ligand containing a thiol group is covalently grafted onto the surface of finely structured ZnO nanorods with a length of 50-250 nm and a diameter of 15-20 nm. Zn-porphyrin is then attached to the ligand molecules by the mechanism of metalligand axial coordination. The resulting energy band diagram suggests that the porphyrin-modified ZnO nanorods might provide an efficient pathway for energy transfer upon being applied to photovoltaic devices.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4247-4252
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• 2011

The porphyrin-incorporated arylether dendrimers ZnP-D1 and ZnP-D4 were investigated to discover the influence of dendritic environments for the axial ligation of pyridine and photoinduced electron transfer by methyl viologen. Absorption and fluorescence spectra of ZnP, ZnP-D1, and ZnP-D4 were measured in dichloromethane with the addition of pyridine or methyl viologen dichloride. Axial ligation of pyridine was confirmed by red-shifted absorption spectrum. The complex formation constants $K_f$ (Table 1) for axial coordination of pyridine on ZnP, ZnP-D1, and ZnP-D4 were estimated to be $4.4{\times}10^3\;M^{-1}$, $3.3{\times}10^3\;M^{-1}$, and $1.7{\times}10^3\;M^{-1}$, respectively. The photoinduced electron transfer to methyl viologen dichloride was confirmed by fluorescence quenching. Stern-Volmer constants Ksv for ZnP, ZnP-D1, and ZnP-D4 were calculated to be $2.6{\times}10^3$, $2.5{\times}10^3$, and $2.1{\times}10^3$, respectively. ZnP-D4 surrounded by 4 aryl ether dendrons shows the smallest $K_f$ and Ksv values, with comparison to ZnP and ZnP-D1.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2598-2602
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• 2010

Two 3-D zinc framework compounds, $[Zn_6(BTB)_4(4,4'-bipy)_4(H_2O)_4]{\cdot}9H_2O$ (1) and $[Zn_3(BTB)_2(4,4'-bipy)_2(H_2O)_2]{\cdot}5H_2O$ (2) ($H_3BTB$ = 1,2,3-benzenetricarboxylic acid, 4,4'-bipy = 4,4'-bipyridine), are obtained from the diffusion method and hydrothermal reaction respectively. Though 1 and 2 has the same coordination geometries of zinc atoms and coordination mode of $BTB^{3-}$, their 2-D layers are different: mirror symmetric layers in 1; parallel ones in 2, further connecting by 4,4'-bipy into 3-D frameworks. The hydrothermal reaction of 2 results in a more stable 3-D framework than the one in 1, which is supported by the single point energy calculations. 1 and 2 show similar blue fluorescence at 417 nm, which can be assigned to LMCT.

• Bulletin of the Korean Chemical Society
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• v.30 no.6
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• pp.1401-1404
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• 2009

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3867-3870
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• 2013

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.289-292
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• 2014

• Bulletin of the Korean Chemical Society
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• v.31 no.7
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• pp.2069-2072
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• 2010

• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.2960-2964
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• 2011

The efficient asymmetric hydrosilylation of imines in the presence of polymethylhydrosiloxane has been investigated by screening chiral diamine-zinc complexes. A series of chiral diamine ligands were prepared from optically pure 1,2-diphenyl-1,2-ethanediamine and screened for effectiveness. N-Benzylic substituents were required for high enantioselectivity; ligands with bulky groups or extra coordinating groups such as OH and S lowered the catalytic activity. The level of asymmetric induction was usually in >90% ee range for aromatic imine substrates. A linear correlation between the ee of the ligand and that of the product was observed, indicating the presence of a 1:1 ratio of ligand to metal coordination in the active catalytic complex.