Photochemistry of cis-[Ru(bpy)2(NH3)2]2+ complex, a promising light-activated anticancer agent

IF 1.7 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Russian Chemical Bulletin Pub Date : 2025-05-15 DOI:10.1007/s11172-025-4588-4

A. A. Kokorenko, V. P. Grivin, I. P. Pozdnyakov, A. V. Mikheylis, Yu. A. Belikov, A. A. Melnikov, S. V. Chekalin, D. B. Vasilchenko, E. M. Glebov

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Abstract

Complex cis-[Ru(bpy)₂(NH₃)₂]²⁺ (1) is a promising photo-activated chemotherapy (PACT) agent; however, its photophysical and photochemical properties have been poorly studied. In this work photoreactions of complex 1 in aqueous solutions were studied by means of steady-state photolysis, nanosecond laser flash photolysis, and ultrafast transient absorption spectroscopy. Excitation of 1 in the wavelength range of 254–505 nm results in substitution of two ammonia ligands by water molecules followed by partial dissociation with the formation of complexes cis-[Ru(bpy)₂(H₂O)₂]²⁺ (2) and cis-[Ru(bpy)₂(H₂O)(OH)]⁺ (3), which exist in equilibrium. The quantum yield of photo-aquation is rather low (about 1%) and decreases on going from the UV to visible spectral range. Excitation of complex 1 in the region of the intra-ligand transition (350 nm) results in the formation of vibrationally hot, triplet excited metal-to-ligand charge transfer (³MLCT) state with a characteristic time shorter than 100 fs. The vibrational cooling time was about 3 ps. The thermally equilibrated ³MLCT state decays within 120 ns in two parallel processes, viz., intersystem crossing to the ground state and exchange of NH₃ ligand with a water molecule to give the complex cis-[Ru(bpy)₂(NH₃)(H₂O)]²⁺ (4). Possible reactions of complex 4 include the inverse substitution of water molecule by the ammonia ligand with the restoration of the initial structure of the complex and the exchange of the second NH₃ ligand with a water molecule with the formation of reaction products, viz., complexes 2 and 3. The photochemical properties of complex 1 are independent of the presence of dissolved oxygen in solution, which is favorable for the PACT applications.

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顺式-[Ru(bpy)2(NH3)2]2+配合物的光化学研究

配合物顺式-[Ru(bpy)2(NH3)2]2+(1)是一种很有前途的光活化化疗（PACT）药物；然而，对其光物理和光化学性质的研究却很少。本文采用稳态光解、纳秒激光闪光光解和超快瞬态吸收光谱等方法研究了配合物1在水溶液中的光解反应。在254-505 nm波长范围内激发1，导致两个氨配体被水分子取代，然后部分解离形成顺式-[Ru(bpy)2(H2O)2]2+(2)和顺式-[Ru(bpy)2(H2O)(OH)]+(3)配合物，它们处于平衡状态。光水化的量子产率很低（约1%），并且从紫外光谱到可见光光谱范围减小。在配体内跃迁区（350 nm）激发配合物1，形成振动热、三重态激发的金属到配体电荷转移（3MLCT）态，特征时间短于100 fs。振动冷却时间约为3ps。热平衡态3MLCT在120 ns内通过两个平行过程衰减，即系统间穿越到基态和NH3配体与水分子交换得到顺式-[Ru(bpy)2(NH3)(H2O)]2+(4)。配合物4可能发生的反应包括：氨配体反取代水分子，恢复配合物的初始结构；第二个NH3配体与水分子交换，形成反应产物，即配合物2和3。配合物1的光化学性质与溶液中溶解氧的存在无关，这有利于PACT的应用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Russian Chemical Bulletin 化学-化学综合

CiteScore

2.70

自引率

47.10%

发文量

257

审稿时长

3-8 weeks

期刊介绍： Publishing nearly 500 original articles a year, by leading Scientists from Russia and throughout the world, Russian Chemical Bulletin is a prominent international journal. The coverage of the journal spans practically all areas of fundamental chemical research and is presented in five sections: General and Inorganic Chemistry; Physical Chemistry; Organic Chemistry; Organometallic Chemistry; Chemistry of Natural Compounds and Bioorganic Chemistry.