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 (1R)-(–)-myrtenol (a) and (1R,2S,5R)-(−)-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 ΦF = 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 (ΦΔ = 0.55–0.69).

中文翻译：

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基于单萜的金属酞菁：可持续合成方法和光物理研究

通过常规方法制备了带有外围烷氧基-单萜基团的四取代锌（II）和铜（II）酞菁。对比非常规合成方法（超声波和微波辐射）。(1) 的合成R)-(–)-桃金娘醇 (一种) 和 (1R,2小号,5R)-(-)-薄荷醇（b) 衍生的邻苯二甲腈前体通过ipso-硝基芳族取代反应，使用超声波照射获得最佳条件，这使我们能够在 4.5 小时内实现完全转化，分离产率高达 74%。随后使用 Zn(II) 或 Cu(II) 盐作为金属模板，以及使用常规和非常规加热方法进行单萜基邻苯二甲腈的环四聚。微波辅助合成被证明是最有效的方法，可在 1 小时内提供完全转化，以高达 70% 的分离产率产生目标单萜基金属酞菁。此外，光物理和光化学研究表明，Zn(II) 酞菁的荧光量子产率范围为ΦF =0.27-0.29，而铜（II）酞菁表现出室温磷光。此外，基于单萜的 Zn(II) 酞菁导致高单线态氧量子产率（ΦΔ =0.55–0.69)。