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Zinc(II) complexes of tetrakis-(6,7-quinoxalino)porphyrazine bearing externally appended 2-pyridyl rings: Synthesis, UV-visible spectral behavior and photoactivity for singlet oxygen generation

Maria Pia Donzello

Dipartimento di Chimica, Università di Roma Sapienza, P. le A. Moro 5, I-00185 Rome, Italy

Corresponding author, tel: +39 06-4991-3330, fax: +39 06-490-324.

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Giorgia De Mori

Dipartimento di Chimica, Università di Roma Sapienza, P. le A. Moro 5, I-00185 Rome, Italy

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Elisa Viola

Dipartimento di Scienze, Università della Basilicata, Viale dell'Ateneo Lucano 10, I-85100 Potenza, Italy

Corresponding author.

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Claudio Ercolani

Dipartimento di Chimica, Università di Roma Sapienza, P. le A. Moro 5, I-00185 Rome, Italy

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Giampaolo Ricciardi

Dipartimento di Scienze, Università della Basilicata, Viale dell'Ateneo Lucano 10, I-85100 Potenza, Italy

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https://doi.org/10.1142/S1088424614500874Cited by:5 (Source: Crossref)

Abstract

The synthesis and physicochemical properties of the Zn^II complexes, [Py₈QxPzZn](Py₈QxPz = tetra-2,3-[6,7-di(2-pyridyl)quinoxalino]porphyrazinato dianion), the corresponding octacation [(2-Mepy)₈QxPzZn]⁸⁺ (neutralized by I^- ions), and the heteropentanuclear complex [(PdCl₂)₄Py₈QxPzZn] are presented and discussed. According to their UV-visible spectral data in non aqueous solvents (CHCl₃, pyridine, dimethyl sulfoxide, dimethylformamide), the species exhibit intense absorptions in the Q-band region at 750–770 nm, in line with parallel spectral data observed for the free base [Py₈QxPzH₂], also reported, and the previously investigated Mg^II complex [Py₈QxPzMg(H₂O)]. The observed Q-band position for this series of "quinoxalinoporphyrazine" macrocycles is about 100 nm to the red with respect to the position of the same absorption for the series of the already reported "pyrazinoporphyrazine" analogs. The spectral effects induced by the peripherally appended methyl-pyridinium groups in the octacation [(2-Mepy)₈QxPzZn]⁸⁺ or by exocyclic coordination in the complex [(PdCl₂)₄Py₈QxPzZn] are also considered. Of the investigated Zn^II complexes, [Py₈QxPzZn] and the related octacation [(2-Mepy)₈QxPzZn]⁸⁺ are active in dimethylformamide solution as singlet oxygen photosensitizers, which is of interest for applications in the photodynamic therapy (PDT) of cancer.

Dedicated to Professor Nagao Kobayashi on the occasion of his 65th birthday

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