Self-Assembled Arene-Ruthenium-Based Rectangles for the Selective Sensing of Multi-Carboxylate Anions

Vajpayee, V; Song, YHo; Lee, MinH; Kim, H; Wang, M; Stang, PJ; Chi, KiW

HERO ID

4932992

Reference Type

Journal Article

Year

2011

HERO ID 4932992
In Press No
Year 2011
Title Self-Assembled Arene-Ruthenium-Based Rectangles for the Selective Sensing of Multi-Carboxylate Anions
Authors Vajpayee, V; Song, YHo; Lee, MinH; Kim, H; Wang, M; Stang, PJ; Chi, KiW
Journal Chemistry: A European Journal
Volume 17
Issue 28 (Jul 4
Page Numbers 7837
Abstract   Novel arene-ruthenium [2+2] metalla-rectangles 4 and 5 have been synthesized by self-assembly using dipyridyl amide ligand 3 and arene-ruthenium acceptors (arene: benzoquinone (1), naphthacenedione (2)) and characterized by NMR spectroscopy and ESI-MS. The solid-state structure of 5 was determined by X-ray diffraction and shows encapsulated diethyl ether molecule in the rectangular cavity of 5. The luminescent 5 was further used for anion sensing with the amidic linkage serving as a hydrogen-bond donor site for anions and the ruthenium moiety serving as a signaling unit. A UV/Vis titration study demonstrated that although 5 interacts very weakly with common monoanions as well as with flexible dicarboxylate anions such as malonate and succinate, it displays significant binding affinity (K>103 in MeOH) for rigid multi-carboxylate anions such as oxalate, citrate, and tartrate, exhibiting a 1:1 stoichiometry. It has been suggested that 1:1 bidentate hydrogen bonding assisted by appropriate geometrical complementarity is mainly responsible for the increased affinity of 5 towards such anions. A fluorescence titration study revealed a large fluorescence enhancement of 5 upon binding to multi-carboxylate anions, which can be attributed to the blocking of the photoinduced electron-transfer process from the arene-Ru moiety to the amidic donor in 5 as a result of hydrogen bonding between the donor and the anion.
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Keyword Ions; Spectrum analysis; 2011)