Sciscione Fabiola, Cong Lei, Donzello Maria Pia, Viola Elisa, Ercolani Claudio, Kadish Karl M
Dipartimento di Chimica, Università di Roma Sapienza , P.le A. Moro 5, I-00185 Roma, Italy.
Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
Inorg Chem. 2017 May 15;56(10):5813-5826. doi: 10.1021/acs.inorgchem.7b00418. Epub 2017 Apr 26.
Tetrapyrrolic porphyrazine macrocycles with externally appended 2-pyridyl rings were synthesized and characterized as to their spectroscopic, electrochemical, and photophysical properties. The investigated compounds are represented as [PyPzH], the unmetalated octakis(2-pyridyl)porphyrazine, and the metal complexes [PyPzM], where M is Mg(HO), Cu, Zn, or Co. The spectroscopic properties and the electrochemical behavior of these compounds were examined in solution of polar (pyridine, dimethyl sulfoxide, and dimethylformamide) and nondonor solvents (CHCl, CHCl), and the data were compared with those obtained from earlier studies on the related tetrapyrazinoporphyrazines, [PyTPyzPzM], and the tetraquinoxalinoporphyrazines, [PyQxPzM], also bearing externally 2-pyridyl rings, and characterized by a more extended central π-conjugated macrocyclic framework. The newly synthesized porphyrazines possess good solubility and are present in their monomeric form in all the examined solvents as shown by UV-visible spectra. The unmetalated species and metal derivatives undergo multiple one-electron reductions within the potential range of the nonaqueous examined solvents. The derivatives with nonredox active metal centers could accept four electrons on the conjugated macrocycle, while the Co complex was characterized by a single one-electron oxidation and five reductions in DMSO. The photosensitizer activity for the generation of singlet oxygen was also examined for the Mg(HO) and Zn complexes in DMF, with measured Φ values being, respectively, 0.42 and 0.64, this latter value indicating the Zn species as being a promising material for use as anticancer agent in photodynamic therapy.
合成了带有外部连接的2-吡啶基环的四吡咯卟吩嗪大环化合物，并对其光谱、电化学和光物理性质进行了表征。所研究的化合物包括未金属化的八（2-吡啶基）卟吩嗪[PyPzH]以及金属配合物[PyPzM]，其中M为Mg(HO)、Cu、Zn或Co。在极性溶剂（吡啶、二甲基亚砜和二甲基甲酰胺）和非给电子溶剂（CHCl、CHCl）溶液中研究了这些化合物的光谱性质和电化学行为，并将数据与早期对相关四吡嗪并卟吩嗪[PyTPyzPzM]和四喹喔啉并卟吩嗪[PyQxPzM]的研究数据进行了比较，后者也带有外部2-吡啶基环，且具有更扩展的中心π共轭大环骨架。新合成的卟吩嗪具有良好的溶解性，紫外可见光谱表明它们在所有检测的溶剂中均以单体形式存在。未金属化的物种和金属衍生物在非水检测溶剂的电位范围内经历多次单电子还原。具有非氧化还原活性金属中心的衍生物可在共轭大环上接受四个电子，而Co配合物在二甲基亚砜中表现为单次单电子氧化和五次还原。还对Mg(HO)和Zn配合物在N,N-二甲基甲酰胺中的单线态氧生成光敏剂活性进行了检测，测得的Φ值分别为0.42和0.64，后一个值表明Zn物种有望作为光动力疗法中的抗癌剂。
