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首页> 外文期刊>RSC Advances >The influence of molecular structure on collision radius for optical sensing of molecular oxygen based on cyclometalated Ir(iii) complexes
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The influence of molecular structure on collision radius for optical sensing of molecular oxygen based on cyclometalated Ir(iii) complexes

机译：基于环金属化Ir（iii）配合物的分子氧光学传感中分子结构对碰撞半径的影响

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Three triphenylamine (TPA) substituted cyclometalated Ir( III ) complexes IrA1, IrA2, and IrA3 based on Ir(ppy) _(3) were synthesized and applied as phosphorescent probes for the monitoring of molecular oxygen. The phosphorescence intensity of all the Ir( III ) complexes in tetrahydrofuran (THF) was gradually quenched with an increase of oxygen concentration. The increase of TPA substituents on the meta -position of 2-phenylpyridine (IrA1-IrA3) gradually improved the oxygen sensitivity of cyclometalated Ir( III ) complexes. IrA3 showed the highest oxygen sensitivity in THF with a K ~(app) _(SV) of 204.8 bar ~(?1) and a limit of detection (LOD) of 0.27 mbar. The relationship between molecular structure and the collision radiuses ( σ ) of all the Ir( III ) complexes has been investigated on the basis of the Demas model and the fundamental expression of luminescence quenching systems by oxygen. The ratio of collision radiuses are σ _(IrA1) / σ _(Ir(ppy) _(3) ) = 1.27 ± 0.05, σ _(IrA2) / σ _(Ir(ppy) _(3) ) = 1.72 ± 0.10, and σ _(IrA3) / σ _(Ir(ppy) _(3) ) = 2.13 ± 0.07, respectively. The introduction and increase of TPA substituents can obviously increase the collision radiuses of cyclometalated Ir( III ) complexes which leading to potential oxygen sensitivity. And the incremental effect of collision radiuses caused by the introduction of TPA substituents resulted in outstanding oxygen sensitivity of IrA3. The results demonstrate for the first time evidence between molecular structure and oxygen sensitivity of the emitters for optical sensing.
机译：合成了三种基于Ir（ppy）_（3）的三苯胺（TPA）取代的环金属化Ir（III）配合物IrA1，IrA2和IrA3，并将其用作磷光探针来监测分子氧。随着氧气浓度的增加，所有Ir（III）配合物在四氢呋喃（THF）中的磷光强度逐渐淬灭。 TPA取代基在2-苯基吡啶（IrA1-IrA3）的间位上的增加逐渐提高了环金属化Ir（III）配合物的氧敏感性。 IrA3在THF中显示出最高的氧敏感性，K〜（app）_（SV）为204.8 bar〜（？1），检出限（LOD）为0.27 mbar。在Demas模型和氧发光猝灭系统的基本表达式的基础上，研究了所有Ir（III）配合物的分子结构与碰撞半径（σ）之间的关系。碰撞半径之比为σ_（IrA1）/σ_（Ir（ppy）_（3））= 1.27±0.05，σ_（IrA2）/σ_（Ir（ppy）_（3））= 1.72±分别为0.10和σ_（IrA3）/σ_（Ir（ppy）_（3））= 2.13±0.07。 TPA取代基的引入和增加可明显增加环金属化Ir（III）配合物的碰撞半径，从而导致潜在的氧敏感性。引入TPA取代基引起的碰撞半径的增量效应导致IrA3的出色的氧敏感性。该结果首次证明了用于光学传感的发射器的分子结构和氧敏感性之间的证据。

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