Tetra-2,3-pyrazinoporphyrazines with Externally Appended Pyridine Rings. 9. Novel Heterobimetallic Macrocycles and Related Hydrosoluble Hexacations as Potentially Active Photo/Chemotherapeutic Antican

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• 作者：Maria Pia Donzello ; Daniela Vittori ; Elisa Viola ; Ilse Manet ; Luisa Mannina ; Luciano Cellai ; Sandra Monti ; Claudio Ercolani
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：August 15, 2011
• 年：2011
• 卷：50
• 期：16
• 页码：7391-7402
• 全文大小：1047K
• 年卷期：v.50,no.16(August 15, 2011)
• ISSN：1520-510X

文摘

New homo- and heterobimetallic porphyrazine complexes of general formula [(M鈥睠l₂)LM] (L = tetrakis-2,3-[5,6-di-(2-pyridyl)pyrazino]porphyrazinato dianion), with M = Zn^II, Mg^II(H₂O), or Pd^II in the central cavity and one M鈥睠l₂ unit (M鈥?= Pd^II, Pt^II) peripherally coordinated at the pyridine N atoms of one of the dipyridinopyrazine fragments, were prepared and characterized by elemental analyses and IR/UV鈥搗isible spectroscopy. Related water-soluble salt-like species, carrying the hexacations [(PtCl₂)(CH₃)₆LM]⁶⁺ (neutralized by I^{鈥?/sup> ions), were also prepared and similarly characterized. Retention of clathrated water molecules is a common feature of all the compounds. A detailed 1H and 13C NMR investigation in dimethylformamide (DMF-d₇) and dimethyl sulfoxide (DMSO-d₆) provided useful information on the type of arrangement in the neutral and hexacationic species of the metalated dipyridinopyrazine fragments, in which the metal centers (PdII/PtII) are bound to the pyridine N atoms (鈥減y鈥損y鈥?coordination) with formation of N_2(pyr)PdCl₂ or N_2(pyr)PtCl₂ coordination sites, the latter one featuring a cis-platin-like functionality. Data obtained in DMF solution of the quantum yield (桅_螖) for the generation of singlet oxygen, 1O₂, the cytotoxic agent in photodynamic therapy (PDT), indicate that all the neutral and charged complexes, among them particularly those carrying centrally ZnII or PdII, exhibit excellent photosensitizing properties, this qualifying the externally platinated complexes as potential bimodal PDT/chemotherapeutic anticancer agents. Fluorescence data (桅_F) provided additional information on the photoactivity of all the species studied. The following companion paper describes the observed interaction of the ZnII hexacation [(PtCl₂)(CH₃)₆LZn]6+ with a G-quadruplex (G4) structure of the telomeric DNA sequence 5鈥?d[AGGG(TTAGGG)₃]-3鈥?in water.}