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Synthesis and assessment of CO-release capacity of manganese carbonyl complexes derived from rigid α-diimine ligands of varied complexity

机译:复杂性不同的刚性α-二亚胺配体衍生的羰基锰锰配合物的合成和CO释放能力的评估

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摘要

Four manganese carbonyl complexes of the type [MnBr(CO)3(NˆN)] (NˆN = α-diimine ligands) namely [MnBr(CO)3(bpy)] (>1), [MnBr(CO)3(phen)] (>2), [MnBr(CO)3(dafo)] (>3) and [MnBr(CO)3(pyzphen)] (>4) (where bpy = bipyridine, phen = 1,10-phenanthroline, dafo = 4,5-diazafluoren-9-one and pyzphen = pyrazino[2,3-f][,]-phenanthroline) have been synthesized and structurally characterized. These four complexes containing the fac-[Mn(CO)3] motif release CO upon illumination with low power visible and UV light. The CO release rates and the absorption maxima of the complexes are however very similar despite systematic increase in structural complexity in the rigid α–diimine ligand frames. This is quite in contrary to manganese carbonyl complexes derived from α–diimine ligands in which at least one of the imine functions is not part of the rigid ring systems. Results of this study will provide help in the future design of ligand frames suitable for the syntheses of photoCORMs to deliver CO to biological targets under the control of light.
机译:四种类型为[MnBr(CO)3(NˆN)](NˆN =α-二亚胺配体)的羰基锰配合物,即[MnBr(CO)3(bpy)](> 1 ),[MnBr( CO)3(phen)](> 2 ),[MnBr(CO)3(dafo)](> 3 )和[MnBr(CO)3(pyzphen)]( > 4 )(其中bpy =联吡啶,phen = 1,10-菲咯啉,dafo = 4,5-二氮杂芴-9-one和pyzphen = pyrazino [2,3-f] [,]-菲咯啉)已合成并进行了结构表征。这四种包含fac- [Mn(CO)3]基序的复合物在低功率可见光和紫外光照射下释放出CO。尽管在刚性的α-二亚胺配体框架中系统复杂性的系统增加,但是CO的释放速率和复合物的吸收最大值非常相似。这与衍生自α-二亚胺配体的羰基锰络合物完全相反,在后者中,至少一个亚胺官能团不是刚性环系统的一部分。这项研究的结果将为将来的配体构架设计提供帮助,这些构架适用于photoCORM的合成,以便在光的控制下将CO传递至生物靶标。

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