Excited‐State Dynamics of a Two‐Photon‐Activatable Ruthenium Prodrug

Abstract

We present a new approach to investigate how the photodynamics of an octahedral ruthenium(II) complex activated through two‐photon absorption (TPA) differ from the equivalent complex activated through one‐photon absorption (OPA). We photoactivated a RuII polypyridyl complex containing bioactive monodentate ligands in the photodynamic therapy window (620–1000 nm) by using TPA and used transient UV/Vis absorption spectroscopy to elucidate its reaction pathways. Density functional calculations allowed us to identify the nature of the initially populated states and kinetic analysis recovers a photoactivation lifetime of approximately 100 ps. The dynamics displayed following TPA or OPA are identical, showing that TPA prodrug design may use knowledge gathered from the more numerous and easily conducted OPA studies.

The Development of Ru(II)-Based Photoactivated Chemotherapy Agents

“…Additionally, two-photon absorption has been utilized for photoactivation of Ru(II) complexes, in which the prodrugs are activated by radiation in the PDT window [ 93 , 94 , 95 , 96 ]. Recently, by simply using a pyrene-modified-terpyridine (tpy-Py) as the labile bidentate ligand, Zhou et al designed and synthesized a promising Ru(II) polypyridine complex 44 , which shows dual PACT and PDT activity upon efficient two-photon excitation in the NIR region [ 97 ].…”

Visible Light‐Gated Organocatalysis Using a RuII‐Photocage

“…Photoremovable groups that can be activated by visible light have gained increasing attention in recent years [37, 40] . Among them Ru II ‐polypyridyl complexes, for example, [Ru(bpy) 2 L 2 ] 2+ with bpy=2,2’‐bipyridine, can be found [41–55] . These have been used for example for the phototriggered release of a biologically active ligand L with the aim of visible light‐controlled neurotransmission, [41, 42, 44, 48] antimicrobial activity [55] or cytotoxicity [47, 54] .…”

Advances in Ru(II)-based Photoactivated Chemotherapy Agents

“…2＋ 的释放及其与 DNA 的共价结合 [74] . 此外, Stavros 等 [75] Turro 小组 [77,78] 进一步拓展此类配合物的研究. 通 过在 dppn 配体上引入甲基位阻基团, 降低了 3 Turro 小 组 [79] 近 期 还 报 道 了 配 合 物 [Ru(pydppn)(biq)(py)] 2＋ (44), 其光诱导单齿吡啶配体的 解离效率为 0.0070 (500 nm), 单重态氧量子效率为 0.75.…”