• Rapid Communication in Photoscience
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• v.3 no.3
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• pp.50-52
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• 2014

Rotaxanes have been prepared using benzene-linked bis-porphyrin or bis-zinc porphyrin as a string component and bis-viologen as a macrocyclic ring component. Absorption and fluorescence spectra of rotaxane formed by complexation of two components have been investigated.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.4117-4120
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• 2011

• Rapid Communication in Photoscience
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• v.2 no.2
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• pp.39-41
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• 2013

It is interesting to introduce viologen moiety into photoactive compounds such as porphyrin and anthracene in the study of supramolecular system such as pseudorotaxanes. For the construction of photoactive pseudorotaxane based on porphyrin-viologen-anthracene triad or its zinc derivative threaded with bis-p-phenylene-34-crown-10 macrocycle, porphyrin-viologen-anthracene triad 1 and its zinc derivative zinc porphyrin-viologen-anthracene triad 2 were prepared and their absorption and fluorescence spectral properties were measured.

• Korean Journal of Crystallography
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• v.11 no.3
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• pp.147-150
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• 2000

The complex [CuL}Cl₂·3H₂O(1)(L=2,13-bis(2-hydroxyethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0/sup 1.18/,0/sup 7.12/] docosane) has been synthesized and characterized by X-ray crystallography. 1. crystallized in the monoclinic, space group C2/c, with a=21.647(6)Å, b=8.549(1)Å, c=18.132(5)Å, β=118.58(2)°, V=2946.8(12)ų, Z=4, R₁(wR₂) for 2374observed reflections of [I>2σ(I)] was 0.052(0.187). The centrosymmetric complex 1 has an axially elongated octahedral geometry with four secondary and tertially amines of the macrocycle and tow oxygen atoms of the pendant hydroxyethyl groups.

• Bulletin of the Korean Chemical Society
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• v.35 no.12
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• pp.3459-3464
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• 2014

Synthesis and structural characterization of mercury(II) halides and perchlorate complexes (1-4) of bis-$OS_2$-macrocycle (L) are reported. L reacts with mercury(II) chloride and bromide to yield an isostructural 2D coordination polymers with type $[Hg(L)X_2]_n$ (1: X = Cl and 2: X = Br). In 1, each Hg atom which lies outside the cavity is six-coordinate with a distorted octahedral geometry, being bound to four adjacent ligands via monodentate Hg-S bonds and two remaining sites are occupied by two terminal chlorido ligands to form a fishnet-like 2D structure. When reacting with mercury(II) iodide, L afforded a 1D coordination polymer $\{[Hg_2(L)I_4]{\cdot}CHCl_3\}_n$ (3) in which each exocyclic Hg atom is four-coordinate, being bound to two sulfur donors from different ligands doubly bridging the ligand molecules in a head-to-tail mode. The coordination sphere in 3 is completed by two iodo terminal ligands, adopting a distorted tetrahedral geometry. On reacting with mercury(II) perchlorate, L forms solvent-coordinated 1D coordination polymer $\{[Hg_2(L)(DMF)_6](ClO_4)_4{\cdot}2DMF\}_n$ (4) instead of the anion-coordination. In 4, the Hg atom is five-coordinate, being bound to two sulfur donors from two different ligands doubly bridging the ligand molecules in a side-by-side mode to form a ribbon-like 1D structure. The three remaining coordination sites in 4 are completed by three DMF molecules in a monodentate manner. Consequently, the different structures and connectivity patterns for the observed exocyclic coordination polymers depending on the anions used are influenced not only by the coordination ability of the anions but also by anion sizes.

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.81-85
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• 2002

A new di-N-cyanoethylated 14-membered tetraaza macrocycle 1,8-bis(2-cyanoethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^2)$ and its nickel(II) complex $[NiL^2(OAc)]^+$ have been prepared. The square-planar complex $[NiL^2](C IO_4)_2$ can be prepared by addition of $HClO_4$ to a hot aqueous solution of $[NiL^2(OAc)]^+$ The Ni-N (tertiary amino group) bond distances $(2.008{\AA})$ of $[NiL^2](C IO_4)_2$ are relatively long, and the complex exhibits a d-d transition band at unusually long wavelength (ca. 515 nm). The complex $[NiL^2](C IO_4)_2$ rapidly reacts with acetate ion or ethylenediamine (en) to produce $[NiL^2(OAc)]^+$ or [Ni(en)_3]^{2+}$, respectively, and is readily decomposed in NaOH (0.01 M) solution. The chemical properties of $[NiL^2]^{2+}$ as well as its synthetic procedure are quite different from those for other related 14-membered tetraaza macrocyclic complexes. Effects of the N-cyanoethyl and C-methyl groups on the properties of $L^2$.

• Korean Journal of Crystallography
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• v.10 no.1
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• pp.88-93
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• 1999

The complex [Ni(L)](ClO4)2 (1) (L=2,13-bis(2-pyridylmethyl)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.1807.12]docosane) has been synthesized and characterized by X-ray crystallography. (1) crystallizes in the triclinic, space group P, with a=10.948(2), b=10.948(2), c=14.911(4) , α=93.73(2), β=93.77(2), γ=99.29(2)o, V=1754.8(7) 3, Z=2, R1(wR2) for 5217 observed reflections of [I>2σ(I)] was 0.048(0.099). The coordination environment around nickel(II) ion shows a distorted octahedron with four secondary and tertially amines of the macrocycle and two nitrogen atoms of pyridylmethyl groups.

• Bulletin of the Korean Chemical Society
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• v.20 no.3
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• pp.276-280
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• 1999

The different core-modified porphyrins 21-thia-23-carba-12-aza-5,10-dimesityl-15,20-diphenylporphyrin (6), and their N(12)-methyl derivatives (8) were synthesized by acid-catalyzed [3+1] condensation of the corresponding 16-thia-5,10-dimesityltripyrromethanes and 2,4-bis[(α-hydroxy-α-phenyl)methyl]pyrrole. Spectroscopic evidence indicates the existence of two different tautomeric forms at room temperature in porphyrin (6). A third form of tautomer was observed when the temperature was lowered to 223 K. The most stable tautomer is one in which the nitrogenic proton resides outside the core of the macrocycle. The ratio of the three different tautomers (outer N-H/ two inner N-H, i.e. 6/12/13) was 1/l/0.5 in the case of (6) while the ratio of 1/l/0.3 was observed in the case of (10). In the case of 21-oxa-23-carba-12-aza-5,10,15,20-tetraphenylporphyrin (7), the only stable tautomeric form observed by 1H NMR was the one that nitrogenic proton resides inside the core on

• Bulletin of the Korean Chemical Society
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• v.24 no.3
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• pp.269-273
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• 2003

The synthesis and properties of 2,13-bis(3'-pyridylmethyl) $(L^3)$, 2,13-bis(4'-pyridylmethyl) $(L^4)$, and 2,13-bis(phenylmethyl) $(L^5)$ derivatives of 5,16-dimethyl-2,6,13,17-tetraazatrcyclo$[16.4.0.^{1.18}0^{7.12}]$docosane are reported. The 3- or 4-pyridylmethyl groups of $[ML^3](ClO_4)_2\;or\;[ML^4](ClO_4)_2$ (M = Ni(Ⅱ) or Cu(Ⅱ)) are not involved in coordination, and the coordination geometry (square-planar) and ligand field strength of the complexes are quite similar to those of $[ML^5](ClO_4)_2$, bearing two phenylmethyl pendant arms. However, the complex formation reactions of $L^3\;and\;L^4$ are strongly influenced by the pyridyl groups, which can interact with a proton or metal ion outside the macrocyclic ring. The macrocycle $L^5$ exhibits a high copper(Ⅱ) ion selectivity against nickel(Ⅱ) ion; the ligand readily reacts with copper(Ⅱ) ion to form $[CuL^5]^{2+}$ but does not react with hydrated nickel(Ⅱ) ion in methanol solutions. On the other hand, $L^3\;and\;L^4$ form their copper(Ⅱ) and nickel(Ⅱ) complexes under a similar condition, without showing any considerable metal ion selectivity. The ligands $L^3\;and\;L^4$ react with copper(Ⅱ) ion more rapidly than does $L^5$ at pH 6.4. At pH 5.0, however, the reaction rate of the former macrocycles is slower than that of the latter. The effects of the 3- or 4-pyridylmethyl pendant arms on the complex formation reaction of $L^3\;and\;L^4$ are discussed.

• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.824-829
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• 2002

New di-N-cyanomethylated tetraaza macrocycle 2.13-bis(cyanomethyl)-5.16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^7.12$]docosane $(L^2)$ has been prepared by the reaction of 3, 14-dimethyl-2,6,13,17-tetraazatricyclo $(L^1)$ with bromoacetonitrile. The square-planar complexes $[ML^2](ClO_4)_2(M=Ni(II)$ or Cu(II) can be prepared by the reaction of $L^2$ with the corresponding metal ion in acetonitrile. The cyanomethyl groups of $[ML^2](ClO_4)_2readily$ react with water to $yield[ML^3](ClO_4)_2$ containing pendant amide groups. The trans-octahedral complexes $[ML^4](ClO_4)_2$, in which two imidate ester groups are coordinated to the metal ion, can be also prepared by the reaction of $[ML^2](ClO_4)_2with$ methanol under mild conditions. The hydrolysis and alcoholysis reactions of $[ML^2](ClO_4)_2are$ promoted by the central metal ion, in spite of the fact that the cyanomethyl group is not involved in intramolecular coordination. The reactions are also promoted by a base such as triethylamine but are retarded by an $acid(HClO_4).Interestingly$, the imidate ester groups of $[ML^4]^2$ are unusually resistant to hydrolysis even in 0.1 M $HCIO_4$ or 0.1 M NaOH aqueous solution. Crystal structure of $[NiL^4](ClO_4)_2shows$ that the Ni-N (pendant imidate ester group) bond is rlatively strong; the Ni-N bond distance is shorter then the Ni-N(tertiary) distance and is similar to the Ni-N (secondary) distance.