Özdemir Mücahit, Karapınar Begümhan, Yalçın Bahattin, Salan Ümit, Durmuş Mahmut, Bulut Mustafa
Marmara University, Department of Chemistry, 34722 Kadikoy, Istanbul, Turkey.
Gebze Technical University, Department of Chemistry, 41400 Gebze, Kocaeli, Turkey.
Dalton Trans. 2019 Sep 14;48(34):13046-13056. doi: 10.1039/c9dt02687h. Epub 2019 Aug 13.
In this study, the synthesis of novel 7-hydroxy-3-ethyl-6-hexyl-4-methylcoumarin (1), four respective phthalonitriles; 4-(7-oxy-3-ethyl-6-hexyl-4-methylcoumarin)phthalonitrile (2), 3-(7-oxy-3-ethyl-6-hexyl-4-methylcoumarin)phthalonitrile (3), 4-chloro-5-(7-oxy-3-ethyl-6-hexyl-4-methylcoumarin)phthalonitrile (4), and 4,5-bis(7-oxy-3-ethyl-6-hexyl-4-methylcoumarin)phthalonitrile (5) and their corresponding alpha tetra, beta tetra and beta octa 7-oxy-3-ethyl-6-hexyl-4-methylcoumarin and beta octa 4-chloro-5-(7-oxy-3-ethyl-6-hexyl-4-methylcoumarin) substituted Zn(ii) (6a-9a) and In(iii) Cl (6b-9b) phthalocyanines has been performed. The novel purified compounds were characterized by standard characterization techniques such as elemental analysis, thermal analysis, FT-IR, UV-vis, H-NMR and MALDI-TOF mass spectrometry. All of the obtained phthalocyanines showed lipophilic behaviour with excellent solubility in organic solvents such as acetone, dichloromethane, chloroform, pyridine and ethyl acetate. The fluorescence quenching behaviour was investigated using 1,4-benzoquinone and potassium iodide as quenchers. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yields) properties of these novel phthalocyanines (6a-9a and 6b-9b) were studied in DMF. They produced high singlet oxygen (for example Φ = 0.99 for 7b) and showed appropriate photodegradation (in the order of 10) which is very important for photodynamic therapy (PDT), and thus these phthalocyanines can be used as Type II photosensitizers in PDT applications.
在本研究中，已完成了新型7-羟基-3-乙基-6-己基-4-甲基香豆素（1）、四种相应的邻苯二甲腈；4-（7-氧基-3-乙基-6-己基-4-甲基香豆素）邻苯二甲腈（2）、3-（7-氧基-3-乙基-6-己基-4-甲基香豆素）邻苯二甲腈（3）、4-氯-5-（7-氧基-3-乙基-6-己基-4-甲基香豆素）邻苯二甲腈（4）以及4,5-双（7-氧基-3-乙基-6-己基-4-甲基香豆素）邻苯二甲腈（5）及其相应的α-四聚体、β-四聚体和β-八聚体7-氧基-3-乙基-6-己基-4-甲基香豆素以及β-八聚体4-氯-5-（7-氧基-3-乙基-6-己基-4-甲基香豆素）取代的Zn（ii）（6a - 9a）和In（iii）Cl（6b - 9b）酞菁的合成。通过元素分析、热分析、傅里叶变换红外光谱（FT-IR）、紫外可见光谱（UV-vis）、氢核磁共振（H-NMR）和基质辅助激光解吸电离飞行时间质谱（MALDI-TOF）等标准表征技术对新型纯化化合物进行了表征。所有得到的酞菁均表现出亲脂行为，在丙酮、二氯甲烷、氯仿、吡啶和乙酸乙酯等有机溶剂中具有优异的溶解性。使用1,4-苯醌和碘化钾作为猝灭剂研究了荧光猝灭行为。在二甲基甲酰胺（DMF）中研究了这些新型酞菁（6a - 9a和6b - 9b）的光物理性质（荧光量子产率和寿命）和光化学性质（单线态氧和光降解量子产率）。它们产生高单线态氧（例如7b的Φ = 0.99）并表现出适当的光降解（约为10），这对于光动力疗法（PDT）非常重要，因此这些酞菁可在PDT应用中用作II型光敏剂。
