• 제목/요약/키워드: Macrocycle

검색결과 96건 처리시간 0.024초

Synthesis of a Porphyrin Derivative Covalently linked to Nickel Aza-macrocycle Cemplex

  • Shin, Eun-Ju;Kwak, Chee-Hun
    • Journal of Photoscience
    • /
    • 제9권1호
    • /
    • 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.

  • PDF

The Fluorescence Behavior of the Responsive Macrocycle by Aromatic Imine Molecules

  • Choi, Chang-Shik;Jeon, Ki-Seok;Lee, Ki-Hwan
    • Journal of Photoscience
    • /
    • 제11권2호
    • /
    • 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).

  • PDF

A Smart Fluorescent Macrocycle with Recognition-Ability of the Neutral Molecules

  • Choi, Chang-Shik;Kim, Mi-Kyoung;Jeon, Ki-Seok;Lee, Ki-Hwan
    • Journal of Photoscience
    • /
    • 제11권1호
    • /
    • 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.

  • PDF

A Carbazole-Attached NO2S2-Macrocycle Exhibiting Hg2+ and Cu2+ Selectivity

  • Lee, Seul-Gi;Kang, Eun-Ju;Lee, Shim Sung
    • Bulletin of the Korean Chemical Society
    • /
    • 제34권5호
    • /
    • 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.

Coordination Chemistry of Chlorophylls: Which Side of the Chlorin Macrocycle is Favored for the Ligand Coordination\ulcorner

  • Oba, Toru;Tamiaki, Hitoshi
    • Journal of Photoscience
    • /
    • 제9권2호
    • /
    • 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].

  • PDF

거대고리 화합물을 매질로한 에멀존 액체막게에 의한 중금속이온의 분리 (Separation of the Heavy Metals by macrocycles- mediated Emulsion Liquid Membrane Systems)

  • 정오진
    • 한국환경과학회지
    • /
    • 제2권1호
    • /
    • pp.61-72
    • /
    • 1993
  • [에멀존]계에서 거대고리화합물에 의한 효과적인 수송현상을 두가지 관점에서 논의하였다. 하나는 중금속이온($Cd^{2+}$. $Pb^{2+}$$Hg^{2+}$)을 토루엔막으로 추출하는 경우.만일 금속=거대고리 화합물의 상로작용이 크다면 이 추출효과는 증가한다. 주번째 토루엔-경꼐면에서, 금속이온을 정량적으로 용리시키기 위해서는 금속이온 -Re-cieving Phase와 금속이온-거대고리화합물 사이의 상호작용에 대한 LogK의 사가 충분히 커야한다 첫번째는 거대고리 화합물의 주개원자, 치환제, 그리고 공동반경을 고려함으로써 해결된다. 이 연구의 결과들은 이론과 잘 일치하며, 시료용액의 종류는 에멀존망에 의한 금속이온의 수송현상에 영향을 준다.$SCN^-$,$1^-$$Br^-$이온과 같은 $A^-$이온을 사용할 경구, 수송순서는 $A^-$ 이온의 용매화순서의 크기에 일치하며, 용해도의 차이때문에 금속이온의 소송능력은 Receiving Phase의 화학종 농도의 크기에 영향을 받는다. 이 연구에서는 적당한 실험조건하에서 조절된 토루엔막을 사용함으로써 $Cd^{2+}$, $Pb^{2+}$, 및 $Hg^{2+}$ 이온의 혼합물로부터 각각의 단일이온들을 효과적으로 분리농축할 수 있었다. 그리고 $Cu^{2+}$,$Ni^{2+}$,$Zn^{2+}$,$Fe^{2+}$, 이온들은 중금속이온들을 분히 농축하는데 부분적으로 방해를 하였다. 그러나 알칼리 및 알칼토금속이온은 방해하지 않았다.

  • PDF