Metal Complexes of a Boron-Dipyrromethene (BODIPY)-Tagged N-Heterocyclic Carbene (NHC) as Luminescent Carbon Monoxide Chemodosimeters
Metal Complexes of a Boron-Dipyrromethene (BODIPY)-Tagged N-Heterocyclic Carbene (NHC) as Luminescent Carbon Monoxide Chemodosimeters
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DOI：
10.1002/chem.201405316
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发表时间：
2015-01-12
影响因子：
4.3
通讯作者：
Plenio, Herbert
中科院分区：
文献类型：
--
作者：
Kos, Pavlo;Plenio, Herbert
合成了硼二吡咯亚甲基（BODIPY）功能化的N-杂环卡宾（NHC）配体4的金属配合物。[（4）（SIMes）RuCl_2（ind）]配合物的荧光猝灭（phi=0.003），[（4）PdI_2（Clpy）]的荧光较弱（phi=0.033），[（4）Au I]的荧光较强（phi=0.70）。BODIPY标记的复合物可以在配体交换和配体解离反应后经历荧光团亮度的显著变化。配合物[（4）MX（1，5-环辛烯）]（M=Rh，Ir; X=Cl，I; phi=0.008-0.016）与一氧化碳反应后转化为强荧光配合物[（4）MX（CO）（2）]（phi=0.53-0.70）。Rh和Ir络合物的未淬灭似乎是羰基络合物中Rh或Ir处的电子密度降低的结果。相比之下，用富电子硫醇盐取代[（4）AuI]中的碘代配体会降低BODIPY荧光团的亮度，使BODIPY成为过渡金属配位圈变化的高灵敏度探针。
Several metal complexes with a boron dipyrromethene (BODIPY)-functionalized N-heterocyclic carbene (NHC) ligand 4 were synthesized. The fluorescence in [(4)(SIMes)RuCl2(ind)] complex is quenched (phi=0.003), it is weak in [(4)PdI2(Clpy)] (phi=0.033), and strong in [(4)AuI] (phi=0.70). The BODIPY-tagged complexes can experience pronounced changes in the brightness of the fluorophore upon ligand-exchange and ligand-dissociation reactions. Complexes [(4)MX(1,5-cyclooctadiene)] (M=Rh, Ir; X=Cl, I; phi=0.008-0.016) are converted into strongly fluorescent complexes [(4)MX(CO)(2)] (phi=0.53-0.70) upon reaction with carbon monoxide. The unquenching of the Rh and Ir complexes appears to be a consequence of the decreased electron density at Rh or Ir in the carbonyl complexes. In contrast, the substitution of an iodo ligand in [(4)AuI] by an electron-rich thiolate decreases the brightness of the BODIPY fluorophore, rendering the BODIPY as a highly sensitive probe for changes in the coordination sphere of the transition metal.