The iClick Reaction of a BODIPY Platinum(II) Azido Complex with Electron-Poor Alkynes Provides Triazolate Complexes with Good 1O2 Sensitization Efficiency
The iClick Reaction of a BODIPY Platinum(II) Azido Complex with Electron-Poor Alkynes Provides Triazolate Complexes with Good 1O2 Sensitization Efficiency
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DOI：
10.1021/acs.organomet.0c00128
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发表时间：
2020-04-27
期刊：
影响因子：
2.8
通讯作者：
Schatzschneider, Ulrich
中科院分区：
文献类型：
--
作者：
Peng, Kun;Einsele, Richard;Schatzschneider, Ulrich
反式-[Pt（bodipy）（N-3）（PEt 3）（2）]（bodipy = 4，4-二氟-4-硼杂-3a，4a-二氮杂-s-引达省-8-基; Et =乙基）与乙炔二甲酸二甲酯（DMAD）或F3 C-C C-COOEt在无催化剂的室温iClick反应中反应以提供配合物[Pt（bodipy）]。（三唑（R，R ′））（PEt 3）（2）]，其中R = R ′ = COOCH 3或R = CF 3，R ′ = COOEt。主要产物是N2-配位的三唑，但一些次要信号指向额外的Ni物质以及Pt（PEt 3）（2）部分的一些反式->顺式异构化。使用H-1、F-19和P-31核磁共振光谱进行动力学研究，得出二级速率常数k（2）在（2.5-6.0）x 10（-3）M-1 s（-1）范围内，其中CF 3取代的炔的反应速度比DMAD快。在光激发时，母体叠氮基复合物以及两个三唑产物在三重态群体中表现出相当大的效率。值得注意的是，系统间交叉的效率由iClick反应调节，这也是通过密度泛函理论计算研究的。
trans-[Pt(bodipy)(N-3)(PEt3)(2)] (bodipy = 4,4-difluoro-4-bora-3a,4a-diaza-s-indacen-8-yl; Et = ethyl) reacts with dimethyl acetylenedicarboxylate (DMAD) or F3C-C C-COOEt in a catalyst-free room-temperature iClick reaction to provide the complexes [Pt(bodipy)(triazolate(R,R'))(PEt3)(2)] with R = R' = COOCH3 or R = CF3, R' = COOEt. The main product is the N2-coordinated triazolate, but some minor signals point to an additional Ni species as well as some trans -> cis isomerization of the Pt(PEt3)(2) moiety. Kinetic studies with H-1, F-19, and P-31 NMR spectroscopy gave second-order rate constants k(2) in the range of (2.5-6.0) x 10(-3) M-1 s(-1), with the CF3-substituted alkyne reacting faster than DMAD. Upon photoexcitation, the parent azido complex as well as the two triazolate products exhibit considerable efficiency in the triplet-state population. Notably, the efficiency of intersystem crossing was modulated by the iClick reaction, which was also studied by density functional theory calculations.