• 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.26 no.7
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• pp.1044-1050
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• 2005

The reaction of cis-[Cr([14]-decane)($OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = isothiocyanate ($NCS^-$), azide ($N3^-$) or chloroacetate(caa)} leads to a new cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ (1), cis-[Cr([14]-decane)($N_3)_2]ClO_4$ (2) or cis-[Cr([14]-decane)($caa)_2]ClO_4$ (3). These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two $NCS^-$anions are bonded to the chromium(III) ion via the Ndonor atom in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by 13$^{\circ}$ from the ideal value of 180$^{\circ}$ for a perfect octahedron. The bond angle N-Cr-N between the Cr(III) ion and the two nitrogen atoms of the isothiocyanate ligands is close to 90$^{\circ}$. The bond lengths of Cr-N between the chromium and $NCS^-$groups are 1.964(5) and 2.000(5) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 2073, 1344 and 1684 $cm^{-1}$ attributed to the $NCS^-$, ${N_3}^-$ and caa groups stretching vibrations, respectively.

• Journal of the Korean Chemical Society
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• v.47 no.2
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• pp.104-108
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• 2003

The reaction of $[Cu(L)]Cl_2{\cdot}H_2O(L=3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^{1.18},0^{7.12}]docosane)$ with 2,5-pyridinedicarboxylate(pdc) led to the formation of $[Cu(L)(H_2O)](pdc){\cdot}6H_2O(1)$. The structure was characterized by X-ray crystallography and spectroscopic method. The coordination geometry around the copper atom is a distorted square-pyramid with four secondary amines of the macrocycle occupying the basal sites and a water molecule at the axial position. Intermolecular hydrogen bonds in 1 form a three-dimensional molecular network.

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.348-354
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• 2009

Copper(II) complexes with tetraoxo dithia tetraaza macrocyclic ligands; [18]ane$N_4S_2$: 1,4,10,13-tetraaza-5,9,14,18-tetraoxo-7,16-dithia-cyclooctadecane, [20]ane$N_4S_2$: 1,5,11,15-tetraaza-6,10,16,20-tetraoxo-8,18-dithia-cyclocosane,Bzo2[18]ane$N_4S_2$: dibenzo-1,4,10,13-tetraaza-5,9,14,18-tetraoxo-7,16-dithia-cyclooctadecane, Bzo2[20]ane$N_4S_2$: dibenzo-1,5,11,15-tetraaza-6,10,16,20-tetraoxo-8,18-dithia-cyclocosane; were entrapped in the nanopores of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)copper(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); $[Cu(N-N)_2]^{2+}$-NaY; in the nanopores of the zeolite, and (ii) in situ template condensation of the copper(II) precursor complex with thiodiglycolic acid. The obtained complexes and new host-guest nanocomposite materials; $[Cu([18]aneN_4S_2)]^{2+}-NaY,\;[Cu([20]aneN_4S_2)]^{2+}-NaY,\;[Cu(Bzo_2[18]aneN_4S_2)]^{2+}-NaY,\;[Cu(Bzo_2[20]aneN_4S_2)]^{2+}$-NaY; have been characterized by elemental analysis FT-IR, DRS and UV-Vis spectroscopic techniques, molar conductance and magnetic moment data, XRD and, as well as nitrogen adsorption. Analysis of data indicates all of the complexes have been encapsulated within nanopore of zeolite Y without affecting the zeolite framework structure.

• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.205-213
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• 2009

This study reports on the geometry optimizations and electronic structure calculations for methyl pyropheophorbide (MPPa), tropolonyl methyl pyropheophorbides (TMPPa, ITMPPa), and cationic tropolonyl methyl pyropheophorbides ($TMPPa^+{{\cdot}BF_4}^-,\;ITMPPa^+{{\cdot}BF_4}^-,\;TMPPa^+,\;and\;ITMPPa^+$) using Local Spin Density Approximation (LSDA/ 6-31G*) and the Restricted Hatree-Fock (RHF/6-31G*) level theory. From the calculated results, we found that substituted cationic tropolonyl groups have larger structural effects than those of substituted neutral tropolonyl groups. The order of structural change effects is $ITMPPa^+ > ITMPPa^+{{\cdot}BF_4}^-$ > ITMPPa, as a result of the isopropyl group. Because it is an electron-releasing group, the substituted isopropyl group electronic effect on a 3-position tropolone increases the Highest Occupied Molecular Orbital and Lowest Unoccupied Molecular Orbital (HOMO-LUMO) energy gap. It was constituted that the larger the cationic characters of these photosensitizers, the smaller the HOMOLUMO band gaps are. The orbital energies of the cationic systems and the ions are stronger than those of a neutral system because of a strong electrostatic interaction. However, this stabilization of orbital energies are counteracted by the distortion of chlorin macrocycle, which results in a large destabilization of chlorin-based compound HOMOs and smaller destabilization of LUMOs as shown in TMPPa (ITMPPa), $TMPPa^+{{\cdot}BF_4}^- (ITMPPa^+{{\cdot}BF_4}^-),\;and\;TMPPa^+\;(ITMPPa^+)$ of Figure 6 and Table 6-7. These results are in reasonable agreement with normal-coordinate structural decomposition (NSD) results. The HOMO-LUMO gap is an important factor to consider in the development of photodynamic therapy (PDT).

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.561-567
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• 1993

The twelve macrocycle (L) complexes of cadmium(II) nitrate have been synthesized: $CdL(NO_3)_2$. All the complexes have been indentified by elemental analysis, electric conductivity measurements, IR and NMR spectroscopic techniques. The molar electric conductivities of the complexes in water and acetonitrile solvent were in the range of 236.8-296.1 $cm^2{\cdot}mol^{-1}{\cdot}ohm^{-1}$ at 25$^{\circ}$C. The characteristic peaks of macrocycles affected from Cd(II) were shifted to lower frequencies as compared with uncomplexed macrocycles. A complex with 1,4,8,11-tetrakis(methylacetato)-1,4,8,11-tetraaza cyclodecane (L4) exhibited two characteristic bands such as strong stretching (1646 $cm^{-1})$, and weaker symmetric stretching band (1384 $cm^{-1})$. NMR studies indicated that all nitrogen donor atoms of macrocycles have greater affinity to cadmium(II) metal ion than do the oxygen atoms. The $^{13}$C-resonance lines of methylene groups neighboring the donor atom such as N and S were shifted to a direction of high magnetic field and the order of chemical shifts were $L_1 < L_2 < L_3 < L_6 < L_4$. Also the chemical shifts values were larger than those of methylene groups bridgeheaded in side-armed groups. This result seems due to not only the strong interaction of Cd(Ⅱ) with nitrogen donors according to the HSAB theory, but weak interaction of Cd(Ⅱ) and COO- ions or sulfur which is enhanced by the flexible methylene spacing group in side-armed groups. Thus, each additional gem-methyl pairs of L_3, L_4\;and\; L_6$ macrocycles relative to $L_1, L_2,\;and\;L_5$ leads to an large enhancement in Cd(II) affinity. ^{13}C$-NMR spectrum of the complex with $L_{12}$ (1,5,9,13-tetracyclothiacyclohexadecane-3,11-diol) reveals the presence of two sets of three resonance lines, and intensities of the each resonance line have the ratio of 1 : 2 : 2. This molecular conformation is predicted as structure of tetragonal complex to be formed by coordinating two sulfur atoms and the other two sulfur atoms which is affected by OH-groups.

• Bulletin of the Korean Chemical Society
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• v.13 no.4
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• pp.363-367
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• 1992

The crystal structure of (1,3,6,9,11,14-hexaazatricycol[12.2.1.$1^{6,9}$]octadecane)copper(Ⅱ) perchlorate, Cu($C_{12}H_{26}N_6$)$(ClO_4)_2$, has been determined by the X-ray diffraction methods. The crystal data are as follows: Mr=516.9, triclinic, ${\alpha}=8.572\;(2)$, b=8.499 (3), c=15.204 (3) ${\AA}$, ${\alpha}=80.42\;(5),\;{\beta}=73.57\;(3),\;{\gamma}=69.82\;(4)^{\circ},\;V=994.2\;{\AA}^3,\;D_C=1.726\;gcm^{-3}$, space group $P{\tilde{1}},\;Z=2,\;{\mu}=21.27\;cm^{-1}&, F(000)=534 and T=297 K. The structure was solved by direct methods and refined by full-matrix least-squares methods to and R value of 0.081 for 1608 observed reflections measured with graphite-mono-chromated Mo Ka radiation on a diffractometer. There are two independent complexes in the unit cell. The two copper ions lie at the special positions (1/2, 0, 0) and (0, 1/2, 1/2)and each complex possesses crystallographic center of symmetry. Each Cu ion is coordinated to four nitrogen donors if the hexaazamacrotricyclic ligand and weakly interacts with two oxygen atoms of the perchlorate ions to form a tetragonally distorted octahedral coordination geometry. The Cu_N (sec), Cu_N(tert) and Cu_O coordination distances are 1.985 (14), 2.055 (14) and 2.757 (13) ${\AA}$ for the complex A and 1.996 (10), 2.040 (11) and 2.660 (13) ${\AA}$ for the complex B, respectively. The macrocycles in the two independent cations assume a similar conformation with the average r.m.s. deviation of 0.073 ${\AA}$. Two 1,3-diazacyclopentane ring moieties of the hexaazamacrotricyclic ligand are placed oppositely and almost perpendicularly to the square coordination plane of the ruffled 14-membered macrocycle. The secondary N atoms are hydrogen-bonded to the perchlorate O atoms with distances of 3.017 (23) and 3.025 (19) ${\AA}$ for the complexes A and B, respectively.

• Journal of the Korean Chemical Society
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• v.31 no.2
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• pp.168-177
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• 1987

The equilibria of chemical reaction between $\alpha$-Ni(rac-[14]-decane)$^{2+}$ and polar solvents(L; ANT, MFA, DMSO, DMF, and DMA) have been investigated by the spectrophotometric method at $25^{\circ}C$. (The equilibrium constants($K_1$) of) the first step in ANT, MFA, DMSO, DMF, and DMA were 31.0, 27.5, 21.3 15.9, and 6.4, respectively. The smallness of equilibrium constants ($K_2$) of the second step compared with $K_1$, was observed. $\alpha$-Ni(rac-[14]-dacane)$^{2+}$ + L $\leftrightharpoons$ [$\alpha$-Ni(rac-[14]-decane){\cdot}L]$^{2+}$ : $K_1$.[$\alpha$-Ni(rac-[14]-decane){\cdot}L)$^{2+}$+ L $\leftrightharpoons$ [$\alpha$-Ni(rac-[14]-decane){\cdot}$L_2$)$^{2+}$ :$K_2$. The relationship between d-d absorption energy and half-wave potential of complex ions at ACT was considered. Macrocyclic ligands increasing d-d transition energy caused half-wave potentials of Ni(II)-macrocycle to be shifted more positively. The half-wave potentials for Ni(rac-1[14]7-diene)$^{2+}$, Ni(meso-1[14]7-diene)$^{2+}$, Ni(1[14]4-diene)$^{2+}$, $\alpha$-Ni(rac-[14]-decane)$^{2+}$, ${\beta}-Ni(rac-[14]-decane)$^{2+}$, and Ni(meso-[14]-decane)$^{2+}$ reductions were -1.419, -1.431, -1.450, -1.473, and -1.480 (V vs. SCE), respectively. The d-d transition energies ($\nu_{max},\;cm^{-1}$) of the Ni(meso-[14]-decane)$^{2+}$ isomer were discussed with the dielectric constant (${\varepsilon}/{\varepsilon}_0$) of the various solvents, $\nu_{max}(cm^{-1})$ increased with increasing ${\varepsilon}/{\varepsilon}_0$.

• Journal of the Korean Chemical Society
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• v.37 no.3
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• pp.344-350
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• 1993

25,26,27,28-Tetraacetoxycalix[4]arene·monohydrate is orthorhombic, space group Pbca with a = 14.979(4), b = 15.154(4), c = 27.890(3) ${\AA}$, Z = 8, V = 6330.6 ${\AA}^{-3}$, D$_c$ = 1.28 $g{\cdot}cm^{-3}$, (Mo K${\alpha}$) = 0.71069 ${\AA}$, ${\mu}$ = 0.86 cm$^{-1}$, F(000) = 2600, and R = 0.069 for 3376 unique observed reflections with I > 1.0 ${\sigma}$(I). The structure was solved by direct methods and refined by cascade diagonal least-squares refinement. All the C-H bond lengths(= 0.96 ${\AA}$), the methyl groups and the methylene groups are fixed and refined as the rigid groups with ideal geometry. The macrocycle exists in the 1,3 alternate conformation (by Conforth) making the angles of 110.7, 684, 113.7 and 68.8$^{\circ}$ between the benzene rings and the methylenic mean plane, and four each acetoxy groups are twisted away from their own benzene rings with the angles of 68.2, 97.6, 78.9 and 71.3$^{\circ}$, respectively. The relative dihedral angles between two opposite side of the benzene rings are 135.6$^{\circ}$ for the rings (1) and (3) and 135.2$^{\circ}$ for (2) and (4). A water molecule which has nearly the same height of the methylenic plane of the macrocycle in the c-axis, is located within the distances of 2.942(5) ${\AA}$ from the O(8) atom of the carbonyl group and 2.901 ${\AA}$ from, another O(2)(1/2-x, -1/2＋y, z). The shortest contact between the molecule is 3.193 ${\AA}$ from the O(4) to the C(3)(1/2＋x, 1/2-y,-z).

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1581-1585
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• 2012

Two pyridinecarboxamide dicyanidecobalt(III) building blocks and two mononuclear seven-coordinated macrocycle manganese(II) compounds have been rationally selected to assemble cyanide-bridged heterobimetallic complexes, resulting in three cyanide-bridged $Co^{III}-Mn^{II}$ complexes. Single X-ray diffraction analysis show that these complexes $\{[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}CH_3OH{\cdot}0.5H_2O$ ($\mathbf{1}$), $\{[Mn(L^2)][Co(bpb)]\}ClO_4{\cdot}0.5CH_3OH$ ($\mathbf{2}$) and ${[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}H_2O$ ($\mathbf{3}$) ($L^1$ = 3,6-diazaoctane-1,8-diamine, $L^2$ = 3,6-dioxaoctano-1,8-diamine; $bpb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)benzenate, $bpmb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate) all present predictable one-dimensional single chain structures. The molecular structures of these one-dimensional complexes consists of alternating units of $[Mn(L)]^{2+}$ ($L=L^1$ or $L^2$) and $[Co(L^{\prime})(CN)2]^-$ ($L^{\prime}=bpb2^{2-}$, or $bpmb2^{2-}$), forming a cyanide-bridged cationic polymeric chain with free $ClO_4{^-}$ as the balance anion. The coordination geometry of manganese(II) ion in the three one-dimensional complexes is a slightly distorted pentagonal-bipyrimidal with two cyanide nitrogen atoms at the trans positions and $N_5$ or $N_3O_2$ coordinating mode at the equatorial plane from ligand $L^1$ or $L^2$. Investigation over magnetic properties of these complexes reveals that the very weak magnetic coupling between neighboring Mn(II) ions connected by the diamagnetic dicyanidecobalt(III) building block. A best-fit to the magnetic susceptibility of complex ${\mathbf}{1}$ leads to the magnetic coupling constants $J=-0.084(3)cm^{-1}$.