New encapsulated bis-cyclometalated Ir(III) complexes with very potent anticancer PDT activity
Photodynamic therapy (PDT) has emerged as a promising approach for cancer treatment, due to its abilityto reduce side effects. In the search for luminescent iridium [Ir(C^N)2(N^N)]+ complexes with high abilityto generate ROS (reactive oxygen species) under irradiation, we employed C^N ligands with h...
| Autores: | , , , , , , , , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | Universidad de Castilla-La Mancha |
| Repositorio: | RUIdeRA. Repositorio Institucional de la UCLM |
| OAI Identifier: | oai:ruidera.uclm.es:10578/46628 |
| Acceso en línea: | https://hdl.handle.net/10578/46628 https://pubs.rsc.org/en/content/articlelanding/2025/qi/d5qi00775e |
| Access Level: | acceso abierto |
| Palabra clave: | New encapsulated bis-cyclometalated Ir(III) complexes very potent anticancer PDT activity |
| Sumario: | Photodynamic therapy (PDT) has emerged as a promising approach for cancer treatment, due to its abilityto reduce side effects. In the search for luminescent iridium [Ir(C^N)2(N^N)]+ complexes with high abilityto generate ROS (reactive oxygen species) under irradiation, we employed C^N ligands with highp-expansion (pbpz (4,9,14-triazadibenzo[a,c]anthracene), 1, or pbpn (4,9,16-triazadibenzo[a,c]naphthacene),3) that should lead to long excited state lifetimes. The photophysical properties were significantlyinfluenced by the degree of C^N ligand p-expansion. Complex 1 exhibited a long fluorescence lifetime,matching the triplet lifetime observed in TAS, suggesting delayed fluorescence. In contrast, the additionalring in complex 3 generated two near-HOMO orbitals, increasing the excited state’s LC character andreducing spin–orbit coupling (SOC) and intersystem crossing (ISC). They exhibited a notable ability togenerate 1O2 and O2•-. TD-DFT studies nicely explained the differentiated photophysical properties. Bothcomplexes exhibited significant phototoxicity against human cancer cells in both monolayer and multicellularspheroids models, with complex 1 exhibiting a higher effect. They effectively photogenerated intracellularROS, including O2•-. The mitochondrial accumulation of 1 and its disruption of mitochondrialfunctions were verified. Wound healing and clonogenic assays demonstrated their potential as antimetastaticagents. In general, complexes’ encapsulation significantly facilitated their cellular accumulation andincreased photocytotoxic indexes, with NP1 achieving one of the lowest IC50 values reported in iridiumchemistry. Furthermore, the nanoparticles showed good anticancer activity even in 3D models. Thus, 1and 3 and especially NP1 show great promise as type I and II PDT agents with theragnostic potential. |
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