Department of Chemistry and Pharmacy, Friedrich-Alexander University Erlangen-Nürnberg (FAU), Egerlandstraße 1, 91058 Erlangen, Germany.
Department of Chemistry and Pharmacy, Friedrich-Alexander University Erlangen-Nürnberg (FAU), Egerlandstraße 3, 91058 Erlangen, Germany.
Inorg Chem. 2021 Sep 20;60(18):14230-14237. doi: 10.1021/acs.inorgchem.1c01731. Epub 2021 Aug 17.
Switchable valence tautomeric metal complexes have been long suggested for applications as chemosensors. However, no such molecular sensors have been yet reported. Here, we present a concept for sensing and the first prototype molecular sensor based on valence tautomeric cobalt-dioxolenes. A valence tautomeric cobalt-dioxolene complex [-Co(SQ)(Cat)(stypy)] ⇄ [-Co(SQ)(stypy)] ( = low spin, = high spin, Cat = 3,5-di-tert-butylcatecholate(2-), SQ = one-electron oxidized, benzosemiquinone(1-) form of Cat, stypy = -4-styrylpyridine) has been used as a molecular sensor. The lability of axial stypy ligands of in solution allows us to exchange stypy ligands by dimethyl sulfoxide and simple pyridine analytes in a controllable way, which triggers colorimetric and magnetic responses.
具有可切换价态互变异构的金属配合物一直被认为可用于化学传感器。然而，目前还没有报道这样的分子传感器。在这里，我们提出了一种基于价态互变异构钴-二氧杂环戊烯的传感概念和第一个原型分子传感器。一个价态互变异构的钴-二氧杂环戊烯配合物[-Co(SQ)(Cat)(stypy)] ⇄ [-Co(SQ)(stypy)]（=低自旋，=高自旋，Cat=3,5-二叔丁基儿茶酚酸盐（2-），SQ=单电子氧化，Cat 的苯并半醌（1-）形式，stypy=-4- 乙烯基吡啶）已被用作分子传感器。在溶液中，轴向 stypy 配体的不稳定性使得我们能够以可控的方式通过二甲基亚砜和简单的吡啶分析物交换 stypy 配体，这引发了比色和磁响应。
