Anion selective recognition and sensing by novel macrocyclic transition metal receptor systems. H-1 NMR, electrochemical, and photophysical investigations
Anion selective recognition and sensing by novel macrocyclic transition metal receptor systems. H-1 NMR, electrochemical, and photophysical investigations
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DOI：
10.1021/ja9725099
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发表时间：
1997-12-10
影响因子：
15
通讯作者：
Maestri, M
中科院分区：
文献类型：
--
作者：
Beer, PD;Szemes, F;Maestri, M
一系列新的氧化还原活性和光活性钌（II）和锇（II）联吡啶-，二茂铁-，和钴茂的大环受体具有选择性地通过电化学和光学方法检测阴离子客体物种的双重能力已被制备。7的单晶X射线结构。Cl-，7 . 2Br（-）和13.20Ac（-）突出了氢键和相应的大环空腔尺寸对固态阴离子识别过程的重要性。质子核磁共振滴定研究在氘代DMSO溶液中揭示这些受体形成强大的和显着的选择性配合物与Cl-，H2 PO 4-，和乙酸根阴离子依赖于灵活性，拓扑结构，和大小的受体腔。循环伏安法和方波伏安法的研究表明，这些受体电化学识别Cl-，H2 PO 4-，和醋酸根阴离子。光物理研究表明，在乙腈溶液中Cl-的发射光谱识别显示7-12。与异源双核受体8，9，和12，负责淬灭的发光钌激发态的能量转移过程的速率常数显着降低氯阴离子的存在下。
A series of novel redox-active and photoactive ruthenium(II) and osmium(II) bipyridyl-, ferrocene-, and cobaltocenium-containing macrocyclic receptors with the dual capability of selectively sensing anionic guest species via electrochemical and optical methodologies have been prepared. Single-crystal X-ray structures of 7 . Cl-, 7 . 2Br(-), and 13.20Ac(-) highlight the importance of hydrogen bonding and respective macrocyclic cavity size to the anion recognition process in the solid state. Proton NMR titration studies in deuterated DMSO solutions reveal these receptors form strong and remarkably selective complexes with Cl-, H2PO4-, and OAc- anions dependent upon the flexibility, topology, and size of the receptor cavity. Cyclic and square-wave voltammetric investigations have demonstrated these receptors to electrochemically recognize Cl-, H2PO4-, and OAc- anions. Photophysical studies reveal emission spectral recognition of Cl- in acetonitrile solutions is displayed by 7-12. With the hetero-dinuclear receptors 8, 9, and 12, the rate constants of the energy transfer process responsible for the quenching of the luminescent ruthenium excited state significantly decreased in the presence of chloride anion.