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Monoterpene-based metallophthalocyanines: Sustainable synthetic approaches and photophysical studies

Andreia C. S. Gonzalez

Coimbra Chemistry Centre, Departamento de Química, Universidade de Coimbra, Rua Larga, 3004-535, Coimbra, Portugal

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Liliana Damas

Coimbra Chemistry Centre, Departamento de Química, Universidade de Coimbra, Rua Larga, 3004-535, Coimbra, Portugal

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Rafael T. Aroso

Coimbra Chemistry Centre, Departamento de Química, Universidade de Coimbra, Rua Larga, 3004-535, Coimbra, Portugal

student member in good standing

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Vanessa A. Tomé

Coimbra Chemistry Centre, Departamento de Química, Universidade de Coimbra, Rua Larga, 3004-535, Coimbra, Portugal

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Lucas D. Dias

Coimbra Chemistry Centre, Departamento de Química, Universidade de Coimbra, Rua Larga, 3004-535, Coimbra, Portugal

São Carlos Institute of Physics, University of São Paulo, 13566-590, São Carlos — SP, Brazil

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João Pina

Coimbra Chemistry Centre, Departamento de Química, Universidade de Coimbra, Rua Larga, 3004-535, Coimbra, Portugal

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Rui M. B. Carrilho

Coimbra Chemistry Centre, Departamento de Química, Universidade de Coimbra, Rua Larga, 3004-535, Coimbra, Portugal

E-mail Address: [email protected]

Correspondence to: R. M. B. Carrilho, tel.: +351 239 854 474.

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, and

Mariette M. Pereira

Coimbra Chemistry Centre, Departamento de Química, Universidade de Coimbra, Rua Larga, 3004-535, Coimbra, Portugal

E-mail Address: [email protected]

Correspondence to: M. M. Pereira, tel.: +351 239 854 474.

SPP full member in good standing

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https://doi.org/10.1142/S1088424620500066Cited by:6 (Source: Crossref)

Abstract

Tetra-substituted zinc(II) and copper(II) phthalocyanines bearing peripheral alkoxy-monoterpene groups were prepared by conventional vs. non-conventional synthetic approaches (ultrasound and microwave irradiation). The synthesis of (1 $R)$ -(–)-myrtenol (a) and (1 $R$ ,2 $S$ ,5 $R)$ -( $-)$ -menthol (b) derived phthalonitrile precursors was performed through ipso-nitro aromatic substitution reactions, with optimal conditions being obtained using ultrasound irradiation, which allowed us to achieve full conversions in 4.5 h, with isolated yields up to 74%. The subsequent cyclotetramerization of monoterpene-based phthalonitriles was carried out using Zn(II) or Cu(II) salts as metal templates, and also using conventional and non-conventional heating methods. Microwave-assisted synthesis was shown to be the most efficient approach, providing complete conversions in 1 h, yielding the target monoterpene-based metallophthalocyanines in up to 70% isolated yields. Furthermore, photophysical and photochemical studies revealed that Zn(II) phthalocyanines possess fluorescence quantum yields in the range of $Φ_{F} =$ 0.27–0.29, while Cu(II) phthalocyanines exhibited room temperature phosphorescence. In addition, the monoterpene-based Zn(II) phthalocyanines led to high singlet oxygen quantum yields ( $Φ_{Δ} =$ 0.55–0.69).

Dedicated to Professor Roberto Paolesse on the occasion of his 60th birthday.

Keywords:

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