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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Near-infrared-emitting heteroleptic cationic iridium complexes derived from 2,3-diphenylbenzo[g]quinoxaline as in vitro theranostic photodynamic therapy agents
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Near-infrared-emitting heteroleptic cationic iridium complexes derived from 2,3-diphenylbenzo[g]quinoxaline as in vitro theranostic photodynamic therapy agents

机译：近红外发光的异溶胶铱络合物衍生自2,3-二苯基苯并[G]喹喔啉，如在体外治疗光动力治疗剂

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摘要

Five heteroleptic cationic iridium complexes with a Pi-expansive cyclometalating 2,3-diphenylbenzo[g] quinoxaline (dpbq) ligand (C<^>N ligand) and different diimine ligands (N<^>N ligands) (i.e. 2,2'-bipyridine (bpy, 1), phenanthroline (phen, 2), 2-(2-pyridinyl) quinoline (pqu, 3), 2,2'-bisquinoline (bqu, 4), and 2-(quinolin-2-yl) quinoxaline (quqo, 5)) were synthesized and characterized. The lowest-energy singlet electronic transitions (S-1 states) were mainly dpbq ligand-centred (ILCT)-I-1 (intraligand charge transfer)/(MLCT)-M-1 (metal to ligand charge transfer) transitions mixed with some (1)Pi,Pi* transitions for complexes 1-4 with increased contributions from (LLCT)-L-1 (ligand to ligand charge transfer) in 3 and 4. For complex 5, the S-1 state was switched to the (LLCT)-L-1/(MLCT)-M-1 transitions. All five complexes displayed weak near-infrared (NIR) phosphorescence, with maximal emission output spanning 700-1400 nm and quantum yields being on the order of 10(-3). The triplet state absorptions of 1-4 all resembled that of the [Ir(dpbq)(2)Cl](2) dimer with lifetimes of ca. 400 ns, while the TA spectrum of 5 possessed the characteristics of both the quqo ligand and the [Ir(dpbq)(2)Cl](2) dimer with a bi-exponential decay of ca. 5 mu s and 400 ns. While the photophysics of these complexes differ slightly, their theranostic photodynamic therapy (PDT) effects varied drastically. All of the complexes were biologically active toward melanoma cells. Complexes 2 and 3 were the most cytotoxic, with 230-340 nM activity and selectivity factors for melanoma cells over normal skin fibroblasts of 34 to 40 fold. Complexes 2, 3, and 5 became very potent cytotoxins with light activation, with EC50 values as low as 12-18 nM. This potent nanomolar light-triggered activity combined with a lower dark toxicity resulted in 5 having a phototherapeutic index (PI) margin of almost 275. The bpy coligand led to the least amount of dark toxicity of 1, while phen and pqu produced cytotoxic but selective complexes 2 and 3. The quqo coligand produced the most potent complex 5 for in vitro PDT, both in terms of photocytotoxicity and PI. All Ir(III) complexes exhibited very bright NIR phosphorescence in melanoma cells. The wide range of cytotoxicity and photocytotoxicity effects within a relatively small class of complexes highlights the importance of the identity of the coligand in the biological activity of the p-expansive biscyclometalated Ir(III) complexes, and their bright NIR emission in live cells demonstrates their potential as theranostic PDT agents.
机译：五种异常阳离子铱配合物，具有PI-膨胀的环荷环化2,3-二苯基苯并[G]喹喔啉（DPBQ）配体（C + N配体）和不同的二嘧啶配体（N <^> n配体）（即2,2' - 苯吡啶（BPY，1），菲咯啉（Phen，2），2-（2-吡啶基）喹啉（PQU，3），2,2'-Bisquinoline（BQU，4）和2-（喹啉林-2-基）喹喔啉（QuQO，5））被合成并表征。最低能量单态电效应（S-1状态）主要是DPBQ配体中心（ILCT）-I-1（Intraligand Chirction转移）/（MLCT）-M-1（金属与配体电荷转移）混合的转变（1）PI，PI *复合物1-4的过渡，从（L1CT）-1-1（配体到配体电荷转移）增加3和4中的贡献。对于复杂的5，S-1状态切换到（ LLCT）-L-1 /（MLCT）-M-1转换。所有五种复合物都显示出弱近红外（NIR）磷光，具有跨越700-1400nm的最大排放输出，量子产量约为10（-3）。 1-4的三重态状态吸收均类似于[IR（DPBQ）（2）CL]（2）二聚体的寿命与CA的寿命相似。 400ns，而5的Ta谱具有Quqo配体和[IR（DPBQ）（2）CL]（2）二聚体的特性，具有CA的双指数衰减。 5亩和400 ns。虽然这些复合物的光学药物略微不同，但其治疗光动力学治疗（PDT）效应大幅变化。所有复合物都对黑素瘤细胞进行了生物学上活性。复合物2和3是最具细胞毒性的，具有230-340nm的活性和选择性因子，用于黑色素瘤细胞在正常的皮肤成纤维细胞34至40倍的情况下。复合物2,3和5变成非常有效的细胞毒素，具有光活化，EC50值低至12-18nm。这种有效的纳米摩尔光触发活性与较低的暗毒性相结合，导致5个具有近275的光照指数（PI）裕度。BPY COLIGALD导致1的暗毒性为1，而PHEN和PQU产生细胞毒性但选择性复合物2和3. Quqo Cooligand在光菌毒性和PI方面为体外PDT产生了最有效的5。所有IR（III）复合物在黑素瘤细胞中表现出非常明亮的荧光磷光。相对较小的复合物中的各种细胞毒性和光菌毒性作用凸显了Cooligand在P-膨胀性Biscycometeralated IR（III）复合物的生物活性中的同一性的重要性，并且其活细胞中的明亮NIR排放证明了它们的潜在的Theranostic PDT剂。

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