Effects of the Peripheral Substituents, Central Metal, and Solvent on the Photochemical and Photophysical Properties of 5,15-Diazaporphyrins
Effects of the Peripheral Substituents, Central Metal, and Solvent on the Photochemical and Photophysical Properties of 5,15-Diazaporphyrins
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外围取代基、中心金属和溶剂对5,15-二氮杂卟啉光化学和光物理性质的影响
DOI：
10.1002/cplu.201900087
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发表时间：
2019
期刊：
影响因子：
3.4
通讯作者：
and Yoshihiro Matano
中科院分区：
文献类型：
--
作者：
Satoshi Omomo;Ryosuke Fukuda;Tomoaki Miura;Tatsuya Murakami;Tadaaki Ikoma;and Yoshihiro Matano
合成了3，7，13，17-四（二（4-羧基苯基）氨基）-5，15-二氮杂卟啉（MDAP-COOH; M=Pd，Cu）及其乙酯前体（MDAP-COOEt; M=Pd，Cu）的金属配合物，用作近红外（NIR）光响应光敏剂。在可见光或NIR光照射下，甲苯中的PdDAP-COOEt以优异的量子产率（ΦΔ=0.99）产生单线态氧（1 O2），而CuDAP-COOEt表现出较低的效率（ΦΔ=0.21）。水溶性PdII配合物PdDAP-COOH在胶束溶液中也表现为光敏剂（ΦΔ=0.20）。用瞬态吸收技术测定了这些染料的光物理性质。发现从MDAP-COOR（R=Et，H）的三重态到分子氧的基态的能量转移效率高度依赖于外围取代基、中心金属和溶剂。此外，评价了PdDAP-COOH在NIR光（720 nm）照射下对HeLa细胞的光毒性。 PdDAP-COOH表现出良好的光动力学活性，对照实验证实1 O2作为活性氧物种生成。
Metal complexes of 3,7,13,17‐tetrakis(di(4‐carboxyphenyl)amino)‐5,15‐diazaporphyrin (MDAP‐COOH; M=Pd, Cu) and their ethyl ester precursors (MDAP‐COOEt; M=Pd, Cu) have been synthesized for use as near‐infrared (NIR)‐light‐responsive photosensitizers. Under irradiation with visible or NIR light, PdDAP‐COOEt in toluene generated singlet oxygen (1O2) with an excellent quantum yield (ΦΔ=0.99), whereas CuDAP‐COOEt exhibited a lower efficiency (ΦΔ=0.21). The water‐soluble PdIIcomplex PdDAP‐COOH also behaved as a photosensitizer (ΦΔ=0.20) in a micellar solution. The photophysical properties of these dyes were measured by transient absorption techniques. It was found that the efficiency of the energy transfer from the triplet state of MDAP‐COOR (R=Et, H) to the ground state of dioxygen was highly dependent on the peripheral substituents, the central metal, and the solvent. Furthermore, the phototoxicity of PdDAP‐COOH toward HeLa cells under irradiation of NIR light (720 nm) was evaluated. As expected, PdDAP‐COOH exhibited good photodynamic activity, and control experiments confirmed that1O2was generated as the active oxygen species.