Effects of the Peripheral Substituents, Central Metal, and Solvent on the Photochemical and Photophysical Properties of 5,15‐Diazaporphyrins
Abstract
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 PdII complex 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 that 1O2 was generated as the active oxygen species.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Mar 04, 2019
- Source ID
- 10.1002/cplu.201900087
Entities
People
- Ryosuke Fukuda
- Satoshi Omomo
- Tadaaki Ikoma
- Tatsuya Murakami
- Tomoaki Miura
- Yoshihiro Matano
Organizations
- Intelligence Community Postdoctoral Research Fellowship Program
- Kyoto University
- Niigata University
- Toyama Prefectural University