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Title: Selective recognition of fluoride and acetate by a newly designed ruthenium framework: experimental and theoretical investigations
Authors: KUNDU, T
Issue Date: 2012
Citation: DALTON TRANSACTIONS, 41(15)4484-4496
Abstract: An effective anion sensor, [Ru-II(bpy)(2)(H2L-)](+) (1(+)), based on a redox and photoactive {Ru-II(bpy)(2)} moiety and a new ligand (H3L = 5-(1H-benzo[d]imidazol-2-yl)-1H-imidazole-4-carboxylic acid), has been developed for selective recognition of fluoride (F-) and acetate (OAc-) ions. Crystal structures of the free ligand, H3L and [1](ClO4) reveal the existence of strong intramolecular and intermolecular hydrogen bonding interactions. The structure of [1](ClO4) shows that the benzimidazole N-H of H2L- is hydrogen bonded with the pendant carboxylate oxygen while the imidazole N-H remains free for possible hydrogen bonding interaction with the anions. The potential anion sensing features of 1(+) have been studied by different experimental and theoretical (DFT) investigations using a wide variety of anions, such as F-, Cl-, Br-, I-, HSO4-, H2PO4-, OAc- and SCN-. Cyclic voltammetry and differential pulse voltammetry established that 1(+) is an excellent electrochemical sensor for the selective recognition kof F- and OAc- anions. 1(+) is also found to be a selective colorimetric sensor for F- or OAc- anions where the MLCT band of the receptor at 498 nm is red shifted to 538 nm in the presence of one equivalent of F- or OAc- with a distinct change in colour from reddish-orange to pink. The binding constant between 1(+) and F- or OAc- has been determined to be logK = 7.61 or 7.88, respectively, based on spectrophotometric titration in CH3CN. The quenching of the emission band of 1(+) at 716 nm (lambda(ex) = 440 nm, Phi = 0.01 at 298 K in CH3CN) in the presence of one equivalent of F- or OAc-, as well as two distinct lifetimes of the quenched and unquenched forms of the receptor 1(+), makes it also a suitable fluorescence-based sensor. All the above experiments, in combination with H-1 NMR, suggest the formation of a 1 : 1 adduct between the receptor (1(+)) and the anion (F- or OAc-). The formation of 1 : 1 adduct {[1(+).F-] or [1(+).OAc-]} has been further evidenced by in situ ESI-MS(+) in CH3CN. Though the receptor, 1(+), is comprised of two N-H protons associated with the coordinated H2L- ligand, only the free imidazole N-H proton participates in the hydrogen bonding interactions with the incoming anions, while the intramolecularly hydrogen bonded benzimidazole N-H proton remains intact as evidenced by the crystal structure of the final product (1). The hydrogen bond mediated anion sensing mechanism, over the direct deprotonation pathway, in 1(+) has been further justified by a DFT study and subsequent NBO analysis.
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