• Journal of Photoscience
• /
• v.9 no.1
• /
• pp.9-12
• /
• 2002

A porphyrin derivative covalently tinted to Ni aria-macrocycle complex has been prepared. Absorption spectrum of porphyrin-Ni aria-macrocycle dyad (λ$\^$max/$\sub$a/=227 nm) was observed to similar to a sum of those of tetratolylporphyrin (λ$\^$max/$\sub$a/=419 nm) and Ni aza-macrocycle (λ$\^$max/$\sub$a/=227 nm), indicating no electronic interaction between porphyrin and Ni aza-macrocycle moieties. Fluorescence quantum yield of dyad (${\Phi}$$\sub$f/= 0.10) was same to that of tetratolylporphyrin (${\Phi}$$\sub$f/= 0.10). Photoinduced intramolecular electron transfer or energy transfer from excited porphyrin moiety to Ni(II) aza-macrocycle moiety should be very inefficient in dyad.

• Journal of Photoscience
• /
• v.11 no.32
• /
• pp.71-74
• /
• 2004

The macrocycle L exhibited a switch on-off behavior through the fluorescent responses by aromatic imine molecule 1 (X=H) / trifluoroacetic acid (TFA). In the 'switch on' state, it was supposed that the aromatic imine molecule 1 is in the cavity of macrocycle L and a photoinduced electron transfer (PET) from the nitrogen of azacrown part to the anthryl group is inhibited by the interaction between the aromatic imine molecule 1 and the azacrown part of macrocycle L. In the 'switch off' state, it was supposed that the protonated imine molecule 1 is induced by the continuous addition of TFA and a repulsion between the protonated azacrown part and the protonated imine molecule 1 is occurred. It was considered that this process induces the intermolecular PET from the protonated imine molecule 1 to the anthryl group of macrocycle L because of a proximity effect between the anthryl group and the protonated imine molecule 1. From the investigation of the transient emission decay curve, the macrocycle L showed three components (3.45 ns (79.72%), 0.61 ns (14.53%), and 0.10 ns (5.75%). When the imine molecule 1 was added in the macrocycle L as molar ratio=1:1, the first main component showed a little longer lifetime as 3.68 ns (82.75%) although the other two components were similar as 0.64 ns (14.28%) and 0.08 ns (2.96%). On the contrary, when the imine molecule 3 (X=C1) was added in the macrocycle L as molar ratio=l:1, all the three components were decreased such as 3.27 ns (69.83%), 0.44 ns (13.24%), and 0.06 ns (16.93%). The fluorescent pH titration of macrocycle L was carried out from pH=3 to pH=9. The macrocycle L and C $U^{2+}$- macrocycle L complex were intersected at about pH=5, while the E $u^{3+}$ -macrocycle L complex was intersected at about pH=5.5. In addtion, we investigated the fluorescence change of macrocycle L as a function of the substituent constant ($\sigma$$_{p}$$^{o}$) showing in the para-substituent with electron withdrawing groups (X=F, Cl) and electron donating groups (X=C $H_3$, OC $H_3$, N(C $H_3$)$_2$), respectively, as well as non-substituent (X=H).).ctively, as well as non-substituent (X=H).

• Journal of Photoscience
• /
• v.11 no.1
• /
• pp.7-9
• /
• 2004

The synthesized macrocycle L was found to be a smart fluorescent receptor which distinguishable efficiently from various neutral molecules with the functional groups such as the electron donating (X =$CH_3$, N($CH_3$)$_2$ and O$CH_3$) and electron withdrawing groups (X =F and Cl), respectively. In the case of guest molecules containing electron donating groups, the fluorescence of macrocycle L was enhanced in the presence of the guest molecules. On the contrary, in the case of guest molecules containing electron withdrawing groups, it was almost quenched in the presence of those.

• Bulletin of the Korean Chemical Society
• /
• v.17 no.1
• /
• pp.83-85
• /
• 1996

• Bulletin of the Korean Chemical Society
• /
• v.35 no.11
• /
• pp.3357-3359
• /
• 2014

• Bulletin of the Korean Chemical Society
• /
• v.34 no.5
• /
• pp.1429-1434
• /
• 2013

A synthesis and cation-induced fluorescent behavior of the carbazole-attached $NO_2S_2$-macrocycle (L) is described and structurally characterized by single crystal X-ray analysis. The photoluminescence spectrum of L in 80% $CH_3CN/CH_2Cl_2$ displays a peak maximum at 431 nm (blue emission). In the metal-induced fluorometric experiment, L showed a drastic chelation-enhanced fluorescence quenching (CHEQ) effect only with $Hg^{2+}$ and $Cu^{2+}$. In ESI-mass study, a 1:1 stoichiometry for complexation of L with $Hg^{2+}$ was confirmed, suggesting the unique sensing behavior of the proposed ligand L due to the selective complexation affinity for $Hg^{2+}$. The observed results indicate that L is a promising turn-off type fluoroionophore for $Hg^{2+}$ and $Cu^{2+}$ detections. Additionally, the $Ag^+$ complex of the precursor macrocycle was prepared and its solid structure was crystallographically characterized.

• Journal of Photoscience
• /
• v.9 no.2
• /
• pp.362-363
• /
• 2002

Since chlorophyll a and bacteriochlorophyll a are asymmetric molecules, an external ligand can coordinate to the central Mg atom either from the chiorin macrocycle side where the C13$^2$-methoxycarbonyl moiety protrudes (denoting as the 'back' side) or frome the other side (the 'face' side). We investigated which side of the macrocycle is favored for the ligand coordination, by survey of the highly resolved crystal structures of various photosynthetic proteins and theoretical model calculations. It is found that chlorophyll a as well as bacteriochlorophyll a and b in the photosynthetic proteins mostly bind their ligands on the 'back' sides. This finding was confirmed by the theoretical calculations for methyl chlorophyllide a and methyl bacteriochlorophyllide a as models: the 'back' type ligand-(bacterio )chlorophyll complex was more stable than the 'face' type one. The calculations predicted influence of the Cl3$^2$-stereochemistry on the choice of the side of the ligand coordination, which is discussed in relation to the presence of the Cl3$^2$-epimer of chlorophyll a in photosystem I reaction center [I].

• Journal of Environmental Science International
• /
• v.2 no.1
• /
• pp.61-72
• /
• 1993

Result of this study indicate that two criteria must be met in order to have effective macrocycle-mediated transport in these emulsionsystem. First, one must effective extraction of the post transition metals, $Cd^{2+}$. $Pb^{2+}$ and $Hg^{2+}$ , into toluene membrane. The effectiveness of this extraction is greatest if log K values for the metal-macrocycle interaction is large. Second, the ratio of the log K values for the metal ion-receiving phase to the metal ion-macrocycle interaction must be large enough to ensure quantitative stripping of the metal ion at the toluene phase interface. Control of the first step can be obtained by appropriate selection of macrocycle donor atom, substituents, and cavity radius. The second step can be controlled by selecting the proper complexing agent for inclusion in the receiving phase. The order of the transport, when using the several $A^-$ species such as $SCN^-$, $1^-$, $Br^-$ and $Cl^-$ is the order of the changing degree of solvation for $A^-$ and the transport of the metals is also affected by the control of concentration for receiving species because of solubility-differences. In this study, we can seperate each single metal ion from the mixture of $Cd^{2+}$, $Pb^{2+}$, and $Hg^{2+}$ ions by using the toluene membranes controlled by optimized conditions. Transport of the single metal is also very good, and alkaline and alkaline earth metals as interferences ions did not affect the seperation of the metals in this macrocycle-liquid membrances but transition metal ions were partially affected as interferences for the post transition metal ions.

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

• Bulletin of the Korean Chemical Society
• /
• v.33 no.1
• /
• pp.301-304
• /
• 2012