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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Zinc azaphthalocyanines with pyridin-3-yloxy peripheral substituents
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Zinc azaphthalocyanines with pyridin-3-yloxy peripheral substituents

机译:具有吡啶-3-基氧基外围取代基的氮杂酞菁锌

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Phthalocyanines (Pc), which are peripherally substituted with pyridin-3-yloxy groups, have shown promise as sensitizers for photodynamic cancer therapy (PDT). Some aza-analogues (AzaPc) are reported here. Four monomers were synthesized, i.e. 5.6-di(pyridin-3-yloxy)pyrazine-2,3-dicarbonitrile, and three pyrazine-2,3-dicarbonitriles, substituted with pyridin-3-yloxy- in combination with H, Me and Ph groups. Cyclotetramerizations of these monomers with the reagent Zn(quinoline)(2)Cl-2 yielded the targeted ZnAzaPcs in 20-40% yields. The cyclotetramerizations were accompanied, and apparently initiated, by complexation between zinc(II) and the pyridin-3-yloxy groups attached to the pyrazine-dicarbonitriles. Two such zinc(II) complexes were isolated and characterized. Identifications of all new substances were primarily based on NMR spectra, where the pulse techniques COSY, NOESY, HSQC and HMBC were applied. Molecular ions of the ZnAzaPcs were determined by mass spectrometry (MALDI-TOF). The UV-Vis spectra of these macrocycles were as expected, with Q-band absorptions at 630-650 nm and molar extinction coefficients, epsilon, 70 000-100 000. Eight peripheral pyridin-3-yloxy groups induced a small blue shift of the Q-band, from 636 nm for unsubstituted ZnAzaPc, to 630 mn, whereas a red shifted Q-band at 650 nm resulted from the combination of phenyl and pyridin-3-yloxy substituents. Improved solubilities were observed for the unsymmetrical ZnAzaPcs compared to octa(pyridin-3-yloxy)ZnAzaPc.
机译:酞菁(Pc),在外围被吡啶3-yloxy基团取代,已显示出作为光动力癌症治疗(PDT)的敏化剂的希望。这里报道了一些氮杂类似物(AzaPc)。合成了四个单体,即5.6-二(吡啶-3-基氧基)吡嗪-2,3-二腈和三个吡嗪-2,3-二腈,分别被吡啶-3-基氧基-,H,Me和Ph取代组。这些单体与试剂Zn(喹啉)(2)Cl-2的环四聚反应以20-40%的产率产生了目标ZnAzaPcs。锌(II)与连接到吡嗪-二腈的吡啶-3-基氧基之间的络合伴随并显然引发了环四聚作用。分离并表征了两种这样的锌(II)配合物。所有新物质的鉴定均主要基于NMR光谱,其中应用了脉冲技术COSY,NOESY,HSQC和HMBC。 ZnAzaPcs的分子离子通过质谱(MALDI-TOF)确定。这些大环的UV-Vis光谱符合预期,Q波段的吸收为630-650 nm,摩尔消光系数为epsilon,为70 000-100000。八个外围的pyridin-3-yloxy基团引起了一个小的蓝移。 Q波段从未取代的ZnAzaPc的636 nm增长到630 mn,而650 nm的红移Q波段是苯基和吡啶-3-基氧基取代基的组合所致。与八(吡啶-3-基氧基)ZnAzaPc相比,非对称ZnAzaPcs的溶解度得到了改善。

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