Oxygen‐Sensing Chemiluminescent Iridium(III) 1,2‐Dioxetanes: Unusual Coordination and Activity
Oxygen‐Sensing Chemiluminescent Iridium(III) 1,2‐Dioxetanes: Unusual Coordination and Activity
复制标题
氧气 - 传感化学发光铱 (III) 1,2 - 二氧杂环丁烷：不寻常的配位和活性
DOI：
10.1002/anse.202200085
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Lippert, Alexander R.
中科院分区：
文献类型：
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作者：
Kagalwala, Husain N.;Bueno, Lorena;Wanniarachchi, Hashini;Unruh, Daniel K.;Hamal, Khagendra B.;Pavlich, Cyprian I.;Carlson, Graham J.;Pinney, Kevin G.;Mason, Ralph P.;Lippert, Alexander R.
下一代荧光铱1，2-二氧杂环丁烷配合物已经开发出来，它由Schaap的1，2-二氧杂环丁烷支架直接连接到金属中心组成。这是通过用苯基吡啶部分合成修饰支架前体来实现的，所述苯基吡啶部分可以充当配体。该支架配体与铱二聚体[Ir（BTP）2（μ-Cl）]2（BTP=2-（苯并[B]噻吩-2-基）吡啶）的反应产生了异构体，其描绘了通过一个BTP配体的环化碳或有趣的硫原子的连接。其相应的1，2-二氧杂环丁烷在缓冲溶液中显示荧光响应，在600 nm处显示单个红移峰。 这种三重态发射被氧气有效地淬灭，产生碳键和硫化合物的体外Stern-Volmer常数分别为0.1和0.009 mbar− 1。 最后，硫结合的二氧杂环丁烷被进一步用于活小鼠的肌肉组织和肿瘤缺氧的异种移植模型中的氧感测，描绘了探针化学发光穿透生物组织的能力（总通量<106 p/s）。
Next generation chemiluminescent iridium 1,2‐dioxetane complexes have been developed which consist of the Schaap's 1,2‐dioxetane scaffold directly attached to the metal center. This was achieved by synthetically modifying the scaffold precursor with a phenylpyridine moiety, which can act as a ligand. Reaction of this scaffold ligand with the iridium dimer [Ir(BTP)2(μ‐Cl)]2(BTP=2‐(benzo[b]thiophen‐2‐yl)pyridine) yielded isomers which depict ligation through either the cyclometalating carbon or, interestingly, the sulfur atom of one BTP ligand. Their corresponding 1,2‐dioxetanes display chemiluminescent responses in buffered solutions, exhibiting a single, red‐shifted peak at 600 nm. This triplet emission was effectively quenched by oxygen, yielding in vitro Stern‐Volmer constants of 0.1 and 0.009 mbar−1for the carbon‐bound and sulfur compound, respectively. Lastly, the sulfur‐bound dioxetane was further utilized for oxygen sensing in muscle tissue of living mice and xenograft models of tumor hypoxia, depicting the ability of the probe chemiluminescence to penetrate biological tissue (total flux ∼106p/s).