Luminescent ruffled iridium(iii) porphyrin complexes containing N-heterocyclic carbene ligands: structures, spectroscopies and potent antitumor activities under dark and light irradiation conditions†,Chemical Science

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Luminescent ruffled iridium(iii) porphyrin complexes containing N-heterocyclic carbene ligands: structures, spectroscopies and potent antitumor activities under dark and light irradiation conditions†
Chemical Science ( IF 7.6 ) Pub Date : 2018-10-10 00:00:00 , DOI: 10.1039/c8sc02920b
Tsz-Lung Lam _{1,

2,

3,

4,

5} , Ka-Chung Tong _{1,

2,

3,

4,

5} , Chen Yang _{1,

2,

3,

4,

5} , Wai-Lun Kwong _{1,

2,

3,

4,

5} , Xiangguo Guan _{1,

2,

3,

4,

5} , Ming-De Li _{1,

2,

3,

4,

5} , Vanessa Kar-Yan Lo _{1,

2,

3,

4,

5} , Sharon Lai-Fung Chan _{5,

6,

7,

8} , David Lee Phillips _{1,

2,

3,

4,

5} , Chun-Nam Lok _{1,

2,

3,

4,

5} , Chi-Ming Che _{1,

2,

3,

4,

5}

Affiliation

A panel of iridium(III) porphyrin complexes containing axial N-heterocyclic carbene (NHC) ligand(s) were synthesized and characterized. X-ray crystal structures of the bis-NHC complexes [Ir^III(ttp)(IMe)₂]⁺ (2a), [Ir^III(oep)(BIMe)₂]⁺ (2d), [Ir^III(oep)(IⁱPr)₂]⁺ (2e) and [Ir^III(F₂₀tpp)(IMe)₂]⁺ (2f) display ruffled porphyrin rings with mesocarbon displacements of 0.483–0.594 Å and long Ir–C_NHC bonds of 2.100–2.152 Å. Variable-temperature ¹H NMR analysis of 2a reveals that the macrocycle porphyrin ring inversion takes place in solution with an activation barrier of 40 ± 1 kJ mol⁻¹. The UV-vis absorption spectra of Ir^III(por)–NHC complexes display split Soret bands. TD-DFT calculations and resonance Raman experiments show that the higher-energy Soret band is derived from the ¹MLCT dπ(Ir) → π*(por) transition. The near-infrared phosphorescence of Ir^III(por)–NHC complexes from the porphyrin-based ³(π, π*) state features broad emission bands at 701–754 nm with low emission quantum yields and short lifetimes (Φ_em < 0.01; τ < 4 μs). [Ir^III(por)(IMe)₂]⁺ complexes (por = ttp and oep) are efficient photosensitizers for ¹O₂ generation (Φ_so = 0.64 and 0.88) and are catalytically active in the light-induced aerobic oxidation of secondary amines and arylboronic acid. The bis-NHC complexes exhibit potent dark cytotoxicity towards a panel of cancer cells with IC₅₀ values at submicromolar levels. The cytotoxicity of these complexes could be further enhanced upon light irradiation with IC₅₀ values as low as nanomolar levels in association with the light-induced generation of reactive oxygen species (ROS). Bioimaging of [Ir^III(oep)(IMe)₂]⁺ (2c) treated cells indicates that this Ir complex mainly targets the endoplasmic reticulum. [Ir^III(oep)(IMe)₂]⁺ catalyzes the photoinduced generation of singlet oxygen and triggers protein oxidation, cell cycle arrest, apoptosis and the inhibition of angiogenesis. It also causes pronounced photoinduced inhibition of tumor growth in a mouse model of human cancer.

中文翻译：

含N-杂环卡宾配体的发光皱纹铱（iii）卟啉配合物：在暗光条件下的结构，光谱学和有效的抗肿瘤活性†

合成并表征了一组包含轴向N-杂环卡宾（NHC）配体的铱（III）卟啉配合物。bis-NHC配合物[Ir ^III（ttp）（IMe）₂ ] ⁺（2a），[Ir ^III（oep）（BIMe）₂ ] ⁺（2d），[Ir ^III（oep）（ I ⁱ Pr）₂ ] ⁺（2e）和[Ir ^III（F ₂₀ tpp）（IMe）₂ ] ⁺（2f）显示了皱纹的卟啉环，中间碳的位移为0.483-0.594Å，长的Ir-C _NHC键为2.100-2.152Å。2a的变温¹ H NMR分析表明，大环卟啉环发生在具有40±1 kJ mol ^-1的激活势垒的溶液中。Ir ^III（por）–NHC配合物的紫外-可见吸收光谱显示出分裂的Soret带。TD-DFT计算和共振拉曼实验表明，较高能量的Soret带是从¹ MLCTdπ（Ir）→π*（por）跃迁得出的。卟啉基³的Ir ^III（por）–NHC复合物的近红外磷光（π，π*）的状态在具有低发射量子产率和较短的寿命701-754纳米设有宽的发射频带（Φ _EM <0.01; τ <4微秒）。物[Ir ^III（POR）（IME）₂ ] ⁺络合物（POR = TTP和OEP）是有效的光敏剂¹ Ò ₂代（Φ_如此= 0.64和0.88），并在仲胺的光诱导的有氧氧化催化活性的和芳基硼酸。bis-NHC配合物对IC ₅₀的癌细胞具有强大的黑暗细胞毒性作用值在亚微摩尔水平。这些复合物的细胞毒性可在光辐照下以低至纳摩尔水平的IC ₅₀值与光诱导产生的活性氧（ROS）结合来进一步增强。[Ir ^III（oep）（IMe）₂ ] ⁺（2c）处理的细胞的生物成像表明，该Ir复合物主要靶向内质网。[Ir ^III（oep）（IMe）₂ ] ⁺催化单线态氧的光诱导产生并触发蛋白质氧化，细胞周期停滞，细胞凋亡和血管生成抑制。它还在人类癌症的小鼠模型中引起明显的光诱导的肿瘤生长抑制。

更新日期：2018-10-10

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