New Ru(ii) photocages operative with near-IR light: new platform for drug delivery in the PDT window.
New Ru(ii) photocages operative with near-IR light: new platform for drug delivery in the PDT window.
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DOI：
10.1039/c8sc02094a
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发表时间：
2018-08-28
期刊：
影响因子：
8.4
通讯作者：
Turro C
中科院分区：
文献类型：
--
作者：
Al-Afyouni MH;Rohrabaugh TN Jr;Al-Afyouni KF;Turro C
设计了一系列含有三齿2，6-二（喹啉-2-基）吡啶（dqpy）配体的Ru（ii）配合物，利用红光/近红外光进行光诱导配体解离.设计了一系列含三齿2，6-二（喹啉-2-基）吡啶（dqpy）配体的Ru（ii）配合物，利用红光/近红外光进行光诱导配体解离.合成了配合物[Ru（dqpy）（L）（CH 3CN）]2+，其中L = 2，2 ′-联吡啶（bpy，1），4，4 ′-二甲基-2，2 ′-联吡啶（Me 2bpy，2），1，10-菲咯啉（phen，3）.配合物1-3的最低能量金属-配体电荷转移（MLCT）吸收峰位于λ 600 nm处，而相应的tpy（2，2 ′;6′，2 ′′-三联吡啶）配合物的MLCT吸收峰位于λ 565 nm处，与λ 455 nm处的MLCT吸收峰形成肩峰。这种偏移归因于当与tpy相比时由dqpy配体提供的较低能量LUMO，如由第一还原波偏移到前者中的约0.3V更正的电势所证明的。此外，在770 nm处观察到[Ru（dqpy）（acac）（CH 3CN）]+（4; acac- =乙酰丙酮化物）的最低MLCT最大值，这归因于由π供体acac-配体的存在提供的HOMO能量的额外增加，并得到计算的支持。配合物1-3在红光（λirr ≥ 610 nm）下发生配体取代反应，配合物4在近红外光（λirr ≥ 715 nm，λ irr = 735 nm）下发生配体取代反应。配合物1-4在450和600 nm照射下表现出相似的配体交换量子产率ΦL，然而，4的量子产率是1-3的2-3倍。这种增强是由不同的HOMO配体的贡献。密度泛函理论计算预测了1-3的MLCT态的部分dqpy ππ* 特征和4的混合Ru/acac- → dqpy金属/配体-配体电荷转移（ML-LCT）态。1-4与穿透组织的红光和近红外光的光反应性，以及它们优异的暗稳定性（>48小时），使得新的Ru（ii）-dqpy平台对于开发用于光诱导药物释放的新络合物和用于需要从紫外和可见光范围到近红外光的广泛吸收的其他应用（例如太阳能转换）是理想的。
A series of Ru(ii) complexes bearing the tridentate 2,6-di(quinolin-2-yl)pyridine (dqpy) ligand was designed to undergo photoinduced ligand dissociation with red/near-IR light. A series of Ru(ii) complexes bearing the tridentate 2,6-di(quinolin-2-yl)pyridine (dqpy) ligand were designed to undergo photoinduced ligand dissociation with red/near-IR light. The complexes [Ru(dqpy)(L)(CH3CN)]2+, where L = 2,2′-bipyridine (bpy, 1), 4,4′dimethyl-2,2′-bipyridine (Me2bpy, 2), and 1,10-phenanthroline (phen, 3). Complexes 1–3 exhibit red-shifted lowest energy metal-to-ligand charge transfer (MLCT) absorption maxima at ∼600 nm, as compared to the corresponding tpy (2,2′;6′,2′′-terpyridine) complexes with MLCT bands at ∼565 nm which appear as shoulders to the MLCT bands at ∼455 nm. This shift is attributed to the lower energy LUMO afforded by the dqpy ligand when compared to tpy, as evidenced by the shift of the first reduction wave to ∼0.3 V more positive potentials in the former. In addition, the lowest MLCT maximum of [Ru(dqpy)(acac)(CH3CN)]+ (4; acac– = acetylacetonate) is observed at 770 nm, attributed to the additional increase in energy of the HOMO afforded by the presence of the π-donating acac– ligand and supported by calculations. Complexes 1–3 undergo ligand substitution upon irradiation with red light, λirr ≥ 610 nm, and the ligand substitution photochemistry of 4 is accessible with near-IR light, λirr ≥ 715 nm and λirr = 735 nm. Complexes 1–4 exhibit similar quantum yields of ligand exchange, ΦL, with 450 and 600 nm irradiation, however, that of 4 is 2–3 times greater than those measured for 1–3. This enhancement is explained by the difference in ligand contributions to the HOMO. Density functional theory calculations predict partial dqpy ππ* character in the MLCT states of 1–3 and a mixed Ru/acac– → dqpy metal/ligand-to-ligand charge transfer (ML-LCT) state in 4. The photoreactivity of 1–4 with tissue-penetrating red and near-IR light, together with their exceptional dark stability (>48 h), makes the new Ru(ii)-dqpy platform ideal for the development of new complexes for photoinduced drug release and for other applications that require broad absorption from the ultraviolet and visible ranges into the near-IR, such as solar energy conversion.
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影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
影响因子：
2.9
作者：
Knoll, Jessica D.;Albani, Bryan A.;Turro, Claudia
通讯作者：
Turro, Claudia
影响因子：
4.6
作者：
HECKER, CR;FANWICK, PE;MCMILLIN, DR
通讯作者：
MCMILLIN, DR
影响因子：
3.2
作者：
Bertrand, Helene;Bombard, Sophie;Teulade-Fichou, Marie-Paule
通讯作者：
Teulade-Fichou, Marie-Paule
影响因子：
20.6
作者：
Knoll JD;Turro C
通讯作者：
Turro C