Dipyrrolyl-functionalized bipyridine-based anion receptors for emission-based selective detection of dihydrogen phosphate

Dipyrrolyl-functionalized bipyridine-based anion receptors for emission-based selective detection of dihydrogen phosphate
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DOI:
10.1002/chem.200601514
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发表时间:
2007-01-01
影响因子:
4.3
通讯作者:
Sessler, Jonathan L.
Sessler, Jonathan L.
中科院分区:
化学2区
文献类型:
--
作者:
Plitt, Patrick;Gross, Dustin E.;Sessler, Jonathan L.

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新的阳离子阴离子受体,基于使用吡咯取代的联吡啶和协调过渡金属,进行了描述。具体而言,聚吡啶-钌和-铑核已被官能化以产生阴离子结合位点。选择该设计以探测吡咯-吡咯分离对阴离子结合亲和力和选择性的影响;该距离在本报告的新系统(受体I和2)中相对于存在于相关的基于二吡咯基喹喔啉的受体3和4中的距离更大。溶液相阴离子结合的研究,通过H-1 NMR光谱滴定在[D-6]DMSO和等温滴定量热法(ITC)在DMSO中进行,揭示了I和2结合最简单的阴离子,具有显着更高的亲和力比3或4。在氯阴离子的情况下,结构的研究,通过单晶X-射线衍射分析进行,是一致的溶液相的结果,并显示,受体I和2都能够稳定络合物与这种卤素阴离子在固态。
New cationic anion receptors, based on the use of pyrrole-substituted bipyridine and coordinated to transition metals, are described. Specifically, polypyridine-ruthenium and -rhodium cores have been functionalized to generate an anion binding site. The design was chosen to probe the influence of the pyrrole-to-pyrrole separation on anion-binding affinities and selectivities; this distance is greater in the new systems of this report (receptors I and 2) relative to that present in related dipyrrolyl quinoxaline based receptors 3 and 4. Solution-phase anion-binding studies, carried out by means of H-1 NMR spectroscopic titrations in [D-6]DMSO and isothermal titration calorimetry (ITC) in DMSO, reveal that I and 2 bind most simple anions with substantially higher affinity than either 3 or 4. In the case of chloride anion, structural studies, carried out by means of single-crystal X-ray diffraction analyses, are consistent with the solution-phase results and reveal that receptors I and 2 are both able to stabilize complexes with this halide anion in the solid state.