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Colorimetric detection of fluoride ion by 5-arylidenebarbituric acids: Dual interaction mode for fluoride ion with single receptor Chinnusamy Saravanan,a Shanmugam Easwaramoorthib and Leeyih Wanga,* 5

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Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x Two 5-arylidenebarbituric acid derivatives (IH and IM) have been synthesized by the Knoevenagel condensation of barbituric acid with 4-N,N-dimethylamino benzaldehyde and studied for anion sensing activities. Both the receptors senses fluoride ion with high selectivity and sensitivity and the sensing action has been evident from the naked eye detection, UV-visible absorption, and fluorescence spectral changes in presence of F-. Indeed, the F- sensing mechanism for receptor IH depends on F- ion concentration. While at higher F- concentrations it forms strong hydrogen bonding interaction with N-H proton of the receptor, at lower concentrations sensing is influenced by the deprotonation of methylene proton, followed by the chemical reaction, which is also confirmed by the 1H-NMR technique. On the other hand, replacing the N-H proton with methyl group, IM does not show any concentration dependent behaviour with F-. The F- concentration dependent sensing is attributed to the changes in the receptoranion interaction equilibrium, where at higher F- concentrations, F- interacts with receptor through hydrogen bonding and at lower concentrations it induces chemical reaction.

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A growing concern over the impact of anions on environmental and biological systems, considerable attention has been continuously devoted to the design and synthesis of artificial anion receptors possessing high affinity and selectivity.1 Several approaches have been adopted for the improvement of selectivity and sensitivity of artificial receptors, which were mainly classified into five categories based on their mode of operation: (1) appropriately pre-organized N-H, C-H and O-H groups which are capable of interacting with anions through hydrogen bonding,2 (2) recognition through anion-π interactions and single electron transfer (SET) reactions,3 (3) tailoring the acidity of N-H proton which undergo deprotonation in presence of particular anion,4 (4) Lewis acid–base interactions,5 (5) anion induced chemical reactions.6 Indeed, any sensory systems fall into the last two categories has been proven to be highly efficient and sensitive. Generally, any receptor molecule having donoracceptor (D-A) configuration shows broad intramolecular charge transfer (ICT) absorption and emission bands.7 If the negatively charged anionic species binds at the electron-deficient acceptor’s site of D-A receptor system, it would alter the electron withdrawing ability of acceptor which in turn retard the ICT interaction. These changes are often manifested through absorption and fluorescence spectral shifts. The electron accepting barbituric acid derivatives play major role in the field of supramolecular chemistry, medicinal chemistry and non-linear optical materials.8 Recently, Fillaut et al. exploited the anion sensing properties of alkynyl ruthenium barbituric acid derivatives in D-π-A configuration, where the This journal is © The Royal Society of Chemistry [year]

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former acts as a donor (D) and latter acts as an acceptor (A).9 The anionic species binds at the barbituric acid site through hydrogen bonding interaction between the two N-H protons, which leads to the blue shifted absorption by retarding ICT interactions. Replacing the N-H proton with N-methyl group resulted in no sensing activity, this feature underscores that the sensing mechanism is based on the hydrogen bonding interaction between the anion and barbituric acid. Further, Spange et al. have demonstrated that the supramolecular complementary hydrogen bonding interaction between a highly dipolar barbiturate dye (BA) and 2,6-diacetamidopyridine (DAC) has marked effect on the reactivity of the barbiturate with variety of potential nucleophiles.10 It has been revealed that the electronic changes induced by the formation of defined hydrogen bonding complexes can be transmitted to a distant reactive centre of the corresponding molecules. Collectively, these studies have demonstrated two strategies: 1) the anion sensing ability of barbituric acid derivatives is only because of its N-H protons, 2) the reactivity of barbituric acid derivatives can be influenced by the formation of intermolecular hydrogen bonding. X

O X 70

N

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Scheme 1. Synthesis of IH and IM

These observations led us to consider the possible interactions with the anions, if the electron acceptor barbituric acid moiety [journal], [year], [vol], 00–00 | 1

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directly linked to electron donor unit. Thus, we synthesized two 5-arylidenebarbituric acid derivatives by the well-established Knoevenagel condensation of 4-N,N-dimethylamino benzaldehyde and barbituric acid or N-methylated barbituric acid as shown in Scheme 1.

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Experimental Section

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Materials and Methods

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All the chemicals (Aldrich Chemicals) and organic solvents (AR grade) were purchased either from TEDIA or Mallinckrodt and were used without any further purifications. 1H and 13C-NMR spectra were recorded using BRUKER SPECTROSPIN-400 MHz spectrometer at room temperature using CDCl3 or DMSO-d6 as the solvent, and the solvent signal was adopted as an internal standard. The UV-visible absorption and fluorescence spectra were measured using a Jasco-MD-2010 spectrophotometer and Jobin Yvon- Fluorolog-TAU-3 spectrofluorimeter, respectively.

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the hydrogen bonding by means of adding a small amount of methanol to the mixture of IH and F- in DMSO. As expected the colour of IH was restored, which confirms that the interaction between the receptor and anions is through hydrogen bonding.12 On the other hand, mixture of methylated barbituric acid (IM) and anionic (F-, CH3COO-, and H2PO4-) solution becomes irresponsive to the addition of methanol. These observations suggest that different sensing mechanisms might have been followed by IH and IM. While the hydrogen bonding interaction is responsible for F- sensing for IH, for IM, it may either be due to structural changes or chemical reactions induced by the anions.13 Notably, F- and OH- induces a different colour for both IH and IM, which suggests the anion specific interaction between the receptors and anions (Fig. 1).

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UV-visible and Fluorescence titrations

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A 9.2 x 10-6 M solution of receptor, (IH and IM) was prepared in DMSO solvent. 2 mL of this solution was transferred to the cuvette, and an initial UV-visible spectrum was measured. Then, the calculated quantity of anion as their tetrabutyl ammonium salt dissolved in DMSO was added to the receptor solution in 0.1 receptor equivalent steps up to 60 equivalents. Similar experiments were done for the fluorescence titrations.

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Synthesis IH and IM Both the the receptors (IH and IM) were prepared as previously reported well established Knoevenagel condensation method with quantitative yields.11 IH: 1H NMR (DMSO-d6, 400 MHz) δ = 11.05 (s, 1H, NH), 10.92 (s, 1H, -NH), 8.43 (d, 2H, Ar), 8.15 (s, 1H, -C=CH), 6.77 (d, 2H, Ar), 3.12 (s, 6H, -N-(CH3)2) ppm. 13C NMR (DMSO-d6, 100 MHz) δ = 165.12, 163.41, 155.92, 154.36, 150.73, 139.52, 120.46, 111.68, 109.54, 40.21 ppm; IM: 1H NMR (DMSO-d6, 400 MHz) δ = 8.44 (d, 2H, Ar), 8.16 (s, 1H, C=CH), 6.76 (d, 2H, Ar), 3.25 (s, 6H, 2N-CH3), 3.12 (s, 6H, -N(CH3)2) ppm. 13C NMR (DMSO-d6, 100 MHz) δ = 163.04, 160.93, 156.18, 154.13, 151.32, 139.03, 131.25, 120.14, 101.00, 39.65, 28.30, 27.61 ppm.

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Results and Discussion 40

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The receptors IH and IM were prepared by the Knoevenagel condensation method as previously reported11 and appeared as dark orange coloured solids. To test the sensing action of the receptors towards the anions, 60 equivalents of various anions in the form of their tetrabutylammonium (TBA) salt was added to receptor solution. As can be seen from the photographs of the solutions given in Figure 1, the green coloured solution of IH becomes pale green by the addition of F-. On the other hand, the green coloured solution of IM becomes colourless in the presence of F-, CH3COO-, and H2PO4- ions. This observed result is quite surprising and is in sharp contrast to the reported result where the methyl analogue of barbituric derivative was insensitive to the Fanions.9 Thus, it can be concluded that the N-H protons in the barbituric acid is not the only reason for anion sensing. To confirm these observations, an attempt has been made to break 2 | Journal Name, [year], [vol], 00–00

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Figure 1. Colour changes observed upon addition of various anions as their TBA salts to the DMSO solution of IH and IM (9.2 x 10-6 M).

The anion sensing ability of the receptors was further probed by the UV-visible absorption spectroscopy. As shown in Figure 2, IH and IM show the characteristic ICT absorption band, due to charge transfer from N,N-dimethylamino moiety to barbituric acid, at 464 and 468 nm respectively.14 Upon addition of 60 molar equivalents of various anions, (F-, Cl-, Br-, I-, NO3-, HSO4-, H2PO4-, CH3COO-) to the DMSO solution of IH, the ICT band at 464 nm has been shifted to 416 nm only in the presence of F-. This blue shifted ICT absorption ca. 48 nm is probably due to the formation of strong hydrogen bond between F- and the N-H protons in IH.9 Though, remaining anions do not perturb the absorption peak position, the absorbance value was found to be decreased to a significant extent in the presence of H2PO4- and CH3COO- ions probably due to the weak hydrogen bonding interactions. For, receptor IM, the ICT band at 468 nm becomes completely disappeared in the presence of F-, CH3COO-, and H2PO4- ions. Notably, the absorption spectrum of IM in the presence of F- is distinctly different from that of IM with CH3COO- and H2PO4-, where the latter generates new absorption feature centered at 340 nm. This observation suggests that the nature of interaction between IM and F- has been different from that of CH3COO- and H2PO4- ions. Indeed, it has been reported that derivative of IH undergoes retro-Knoevenagel reaction by the hydrolytic cleavage of C=C bond and forms corresponding 4diarylaminobenzaldehyde and barbituric acid derivative, where the former absorbs at 340 nm.15 Thus, we can conclude that the appearance of new band at 340 nm for IM with H2PO4- and CH3COO- ions might be due to the cleavage of IM into corresponding barbituric acid and 4-dimethylaminobenzaldehyde, which in fact can be seen even by the naked eye i.e. change of colour from light green to colourless. Further, as shown in the Figure 2, the absorption pattern of IH and IM in the presence of This journal is © The Royal Society of Chemistry [year]

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base is different from the other anions studied here, which indicates that the receptor-anion interaction is characteristic to the nature of anions, its structure, basicity etc., and no common interaction mode has been derived in this case.

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absorbance around 342 nm has been noted for 1H in the presence of some of the anions, however the spectral position of intense, low energy peak remains unperturbed even after 24 hours. Further, the anion binding experiments at different 1H concentration up to 5.52 x 10-5 M were carried out to probe the concentration effect and no significant difference has been found (see ESI S2 and S3†). These experiments suggest that the fluoride ion concentration dependent behaviour would probably been due to the alternations in the chemical equilibrium that exists between the receptor and anion.To understand the concentration of F- on H and F- interaction, the absorption spectra were measured by adding F- in 10, 20, 30, 40, 50, 100, 150 equivalents in one shot ([IH]=9.2 x 10-6 M). As can be seen in Figure 3, the peak at 416 nm started to appear when the F- concentration is about ten times higher than that of IH and becomes gradually intensed with further addition of F- till it reaches 40 equivalents. 0.6

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Figure 2. UV-vis absorption spectra of IH and IM (9.2 x 10-6 M) upon addition of F-, Cl- Br-, I-, H2PO4-, HSO4-, NO3- and CH3COO- ions (as TBA salts) in DMSO.

The receptor-anion binding nature has been gleaned from systematic UV-visible, fluorescence and 1H-NMR titration experiments. To our surprise, for IH, upon gradual addition of F-, the ICT band at 464 nm progressively decreases at the expense of new peak at 300 nm; when the concentration of F- reaches 60 molar equivalents of receptor concentration the solution becomes colourless (Fig. 3). The isobestic point at 400 nm confirms the existence of only two components in the reaction mixture. Interestingly, this behaviour is in sharp contrast with the previous experiment, where the 60 equivalent addition of F- to 1H, in one shot generates new absorption peak at 416 nm (Fig. 2). The reason behind this F- concentration dependent behaviour would either be due to the different equilibrium reactions that occur at distinct concentration levels or difference in the time duration of the experiments. The step wise titration experiments generally take longer time than the one shot addition, which may alters the binding interaction. In order to analyze the time factor on this issue, the UV-visible absorption spectra of the solutions of IH with various anions were measured in different time intervals and the spectrum measured after 24 hours is given in Figure S1 (See ESI S1†). As shown in the Figure S1, changes in the relative This journal is © The Royal Society of Chemistry [year]

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This observed feature reveals that upon addition of more than 10 equivalents of F- by one shot, the F- forms strong hydrogen bond with the N-H protons of barbituric acid group, subsequently reduces its electron withdrawing power and thereby blue-shifts the peak maximum from 464 to 416 nm.9 Conversely, when the receptor was present at higher concentration than F-, the Finduces chemical reaction in IH rather than forming hydrogen bond. The reason behind this behaviour is not clear now, however Journal Name, [year], [vol], 00–00 | 3

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absence of N-H protons. Additionally, IM does not give any systematic fluorescence pattern with fluoride ion (see ESI S5†). From the optical and fluorescence titrations, it is confirmed that both IH and IM are capable to sense the F- concentration at a level of less than 10-5 M. Collectively, it can be concluded from the UV-Visible and fluorescence spectral patterns of IH and IM that 1) the sensitivity of IH towards F- is mainly depending on the F- concentration, 2) the N-H proton in IH plays a key role in the sensing the anion, and 3) the sensitivity of IM towards anion is mainly due to the anion induced chemical reactions. In the case of IM, the presence of one equivalent F- does not yield any changes in 1H NMR spectrum (see ESI S8†). At the second equivalent of addition, the singlet at 9.67 ppm corresponding to the aldehyde proton emerges similar to IH. Moreover, the doublet at 5.30 ppm confirms the generation of double addition product. Upon further F- addition, the intensity of aldehyde proton and the double addition product peak gradually increases, as shown in Figure. 4.

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Scheme 2. Plausible route for the formation of double addition product.

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Figure 6. Fluorescence spectra of IH (9.2 x 10 M) in DMSO A) upon addition of F- by gradually and B) upon addition of various equivalents of F- by one shot.

This hypothesis has further been supported by the fluorescence titration experiments with IH upon gradual addition of F-. In concurrence with the UV-visible absorption spectral studies, Fconcentration dependent fluorescence pattern has been noted for IH as shown in Figure 6. Upon gradual addition of F- up to 60 equivalents, when excited at its absorption maximum, the fluorescence maximum for IH at 518 nm decreases with appearance of one small shoulder at 493 nm as shown in Figure 6A. Conversely, at higher F- concentrations, the peak at 493 nm started appearing and becomes intense with increasing concentration of F- as shown in Figure 6B. This result also proves F- concentration dependent sensitivity of IH. In contrast, IM does not show such concentration dependant UV-visible absorption and fluorescence patterns with any of the tested anions due to the This journal is © The Royal Society of Chemistry [year]

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In presence of 7 equivalents of F-, IM shows a broad peak at 16.5 ppm (see ESI S8†) corresponding to the formation of [HF2]-. This is due to the fact that F- abstracts the proton from the methylene group of barbituric acid. Furthermore, four different chemically equivalent methyl groups at 3.05, 3.03, 2.99 and 2.80 ppm are well accounted with the corresponding NMR spectrum (see ESI S8†). Based on the above facts, a tentative mechanism for the formation of double addition product has been depicted in scheme 2. Finally, it is proved that upon addition of F- ion in excess forms hydrogen bond with N-H protons of the barbituric acid that in turn prevents the cleavage of IH into corresponding aldehyde and barbituric acid;10 upon addition of F- at lower concentration levels, it induces retro-Knoevenagel reaction by cleaving the C=C of IH into corresponding aldehyde and barbituric acid. IM does not show such a concentration dependant interaction with F- due to the absence of N-H protons.

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We have demonstrated the anion sensing ability of two easily synthesizable 5-arylidenebarbituric acid derivatives (IH and IM). When compared to IM, IH shows good selectivity for F- ion over the other tested anions. Particularly, in presence of lower Flimits, the sensing is through the anion induced chemical reaction where the receptor IH is disassociated into corresponding aldehyde and barbituric acid by virtue of retro-Knoevenagel Journal Name, [year], [vol], 00–00 | 5

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The decreased intensity of olefinic proton is probably due to the alteration of acceptor strength by the formation of strong hydrogen bond between N-H and F-, which reduces the double bond character of olefinic protons. Even though the F- forms strong hydrogen bond with N-H protons, an indication for the double addition product can been seen in 1H-NMR spectra (the asterisk in the Fig. 5). This is due to the fact that upon addition of excess F- by one shot not all the F- forms strong hydrogen bond with N-H protons; some of the F- forms hydrogen bond with water molecule to cleave the IH into corresponding aldehyde and barbituric acids.

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reaction, which leads to double addition product. The excess F-, over 40 times higher than receptor concentration IH forms the strong hydrogen bond with the N-H protons, thereby the ICT absorption band has been blue shifted by 48 nm. We believe that the concentration dependent, sensitive, and selectivity towards Fis advantageous in terms of qualitative and quantitative detection of anions. In absence of N-H protons, the anion sensing by IM is due to the F- induced chemical reaction. This kind of alteration of substrate’s reactivity by the formation of supramolecular hydrogen bond interactions between F- and the N-H protons of barbituric acid may open up new prospective in the anion sensing ability of the barbituric acid derivatives.

Acknowledgements 15

The authors thank the National Science Council of Taiwan, Republic of China, for financially supporting this research under Contract No. NSC 96-2113-M-002-012-MY3. The work is also supported by the suprainstitutional project “STRAIT” of CSIRCLRI. This is CSIR-CLRI contribution number 1026.

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Center for Condensed Matter Sciences, National Taiwan University, Taipei, 106, Taiwan, R.O.C. E-mail: [email protected] b Chemical Laboratory, CSIR-Central Leather Research Institute, Adyar, Chennai- 600 020, India † Electronic Supplementary Information (ESI) available: [UV-vis absorption spectra of IH, IM, fluorescence spectra of IM, NMR titration results of IH and IM]. See DOI: 10.1039/b000000x/ 1 (a) F. P. Schmidtchen and M. Berger, Chem. Rev., 1997, 97, 16091646; (b) P. D. Beer and P. A. Gale, Angew. Chem. Int. Ed., 2001, 40, 486-516; (c) P. D. Beer and E. J. Hayes, Coord. Chem. Rev., 2003, 240, 167-189; (d) C. Suksai and T. Tuntulani, Chem. Soc. Rev., 2003, 32, 192-202; (e) R. Martínez-Manêz and F. Sancenón, Chem. Rev., 2003, 103, 4419-4476; (f) A. P. Davis, Coord. Chem. Rev., 2006, 250, 2939-2951; (g) P. A. Gale, Acc. Chem. Res., 2006, 39, 465-475; (h) M. D. Lankshear and P. D. Beer, Acc. Chem. Res. 2007, 40, 657-668; (i) C. Caltagirone and P. A. Gale, Chem. Soc. Rev., 2009, 38, 520-563; (j) S. Kubik, Chem. Soc. Rev., 2009, 38, 585-605. 2 (a) L. S. Evans, P. A. Gale, M. E. Light and R. Quesada, Chem. Commun., 2006, 965-967; (b) S. O. Kang, R. A. Begumand and K. Bowman-James, Angew. Chem. Int. Ed. 2006, 45, 7882-7894; (c) V. Santacroce, J. T. Davis, M. E. Light, P. A. Gale, J. C. IglesiasSánchez, P. Prados and R. Quesada, J. Am. Chem. Soc., 2007, 129, 1886-1887; (d) V. Haridas, S. Sahu, P. P. P. Kumar and A. R.Sapala, RSC Adv., 2012, 2, 12594–12605; (e) M. Cametti and K. Rissanen, Chem. Soc. Rev., 2013, 42, 2016-2038. 3 (a) S. Guha and S. Saha, J. Am. Chem. Soc., 2010, 132, 17674– 17677; (b) S. Guha, F. S. Goodson, L. J. Corson and S. Saha, J. Am. Chem. Soc., 2012, 134, 13679–13691; (c) Y. Zhao, Y. Li, Z. Qin, R. Jiang, H. Liua and Y. Lia, Dalton Trans., 2012, 41, 13338-13342; (d) M. R. Ajayakumar and P. Mukhopadhyay, Org. Lett., 2010, 12, 2646–2649; (e) M. R. Ajayakumar, G. Hundalb and P. Mukhopadhyay, Chem. Commun., 2013, 49, 7684-7686. 4 (a) X. He, S. Hu, K. Liu, Y. Guo, J. Xu and S. Shao, Org. Lett., 2006, 8, 333-336; (b) P. Rajamalli and E. Prasad, Org. Lett., 2011, 13, 3714–3717; (c) Y. Qu, J. Hua, and H. Tian, Org. Lett., 2010, 12, 3320-3323. 5 (a) C. R. Wade, A. E. J. Broomsgrove, S. Aldridgeand and F. P. Gabbaï, Chem. Rev. 2010, 110, 3958-3984; (b) I-S. Ke, M. Myahkostupov, F. N. Castellano and F. P. Gabba, J. Am. Chem. Soc., 2012, 134, 15309−15311; (c) L. Weber, D. Eickhoff, J. Kahlert, L. Böhling, A. Brockhinke, H-G. Stammler, B. Neumanna and M. A. Foxb, Dalton Trans., 2012, 41, 10328-10346. 6 (a) L. Yu-Chen and C. Chao-Tsen, Org. Lett., 2009, 11, 4858-4861; (b) V. Bhalla, H. Singhand and M. Kumar, Org. Lett., 2010, 12, 628;

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(c) C. Padié and K. Zeitler, New J. Chem., 2011, 35, 994-997; (d) S. Punidha and L. Chang-Hee, J. Org. Chem., 2011, 76, 3820-3828; (e) F. Li, J. Feng-Lei, F. Daniel, D. H. Pierre and L. Yi, Chem. Commun., 2011, 47, 5503-5505; (f) X. Cao, W. Lin, Q. Yu and J. Wang, Org. Lett., 2011, 22, 6098-6101; (g) K. M. Mahoney, P. P. Goswami and A. H. Winter, J. Org. Chem., 2013, 78, 702–705. (a) N. DiCesare and J. R. Lakowicz, Anal. Biochem., 2002, 301, 111116; (b) K. Kobiro and Y. Inoue, J. Am. Chem. Soc., 2003, 125, 421427. (a) Y. Kawabe, H. Ikeda, T. Sakai and K. Kawasaki, J. Mater. Chem., 1992, 2, 1025-1031; (b) Y-W. Caoa, X-D. Chaib, S-G. Chen, Y-S. Jianga, W-S. Yanga, R. Lua, Y-Z. Rena, M. Blanchard-Desceb, T-J. Lia and J-M. Lehn, Syn. Met., 1995, 71, 1733-1734; (c) N. D. McClenaghan, C. Absalon and D. M. Bassani, J. Am. Chem. Soc., 2003, 125, 13004-13005; (d) S. Yagai, T. Kinoshita, M. HigashiK. Kishikawa, T. Nakanishi, T. Karatsu and A. Kitamura, J. Am. Chem. Soc., 2007, 129, 13277-13287; (e) S. Yagai, S. Kubota, H. Saito, K. Unoike, T. Karatsu, A. Kitamura, A. Ajayaghosh, M. Kanesato and Y. Kikkawa, J. Am. Chem. Soc., 2009, 131, 5408-5410; (f) S. Yagai, Y. Goto, T. Karatsu, A. Kitamura and Y. Kikkawa, Chem. Eur. J. 2011, 17, 13657–13660. J-L. Fillaut, J. Andriés, J. Perruchon, J-P. Desvergne, L. Toupet, L. Fadel, B. Zouchoune and J-Y. Saillard, Inorg. Chem., 2007, 46, 5922-5932. (a) I. Bolz, D. Schaarschmidt, T. Rüffer, H. Lang and S. Spange, Angew. Chem. Int. Ed., 2009, 48, 7440–7443; (b) M. Bauer and S. Spange, Eur. J. Org. Chem., 2010, 259–264; (c) M. Bauer and S. Spange, Angew. Chem. Int. Ed., 2011, 50, 9727–9730. (a) B. Jursic, J. Heterocyclic Chem., 2001, 38, 655-657; (b) B. S. Jursic and D. M. Neumann, J. Heterocyclic Chem., 2003, 40, 465474; (c) M. K. Haldar, M. D. Scott, N. Sule, D. K. Srivastava and S. Mallik, Bioorg.& Med. Chem. Lett., 2008, 18, 2373–2376. (a) X. He, S. Hu, K. Liu, Y. Guo, J. Xu and S. Shao, Org. Lett., 2006, 8, 333-336; (b) S. V. Bhosale, S. V. Bhosale, M. B. Kalyankar and S. J. Langford, Org. Lett., 2009, 11, 5418-5421. (a) M. Okutani and Y. Mori, Tetrahedron. Lett., 2007, 48, 6856– 6859; (b) M. Okutani and Y. Mori, J. Org. Chem., 2009, 74, 442 – 444. R. Lu, S-G. Chen, X-D. Chai, Y-W. Cao, W-S Yang, Y-S. Jiang and T-J. Li, Syn. Met., 1995, 71, 2035-2036. (a) R. Ahuja, P-L. Caruso, D. Mobius, W. Paulus, H. Ringsdo and G. Wildburg, Angew. Chem. Int. Ed., 1993, 32, 1033-1036; (b) T. M. Bohanon, S. Denzinger, R. Fink, W. Paulus, H. Ringsdorf and M. Weck, Angew. Chem. Int. Ed., 1995, 34, 58-60. B. S. Jursic, D. M. Neumann, Z. Moore and E. D. Stevens, J. Org. Chem., 2002, 67, 2372-2374.

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Dalton Transactions Accepted Manuscript

DOI: 10.1039/C3DT52824C

Page 7 of 7

Dalton Transactions View Article Online

DOI: 10.1039/C3DT52824C

The sensing ability of F- by one of the barbituric acid derivatives studied here is highly depending on the way of addition of F-. Upon addition of excess amount of F- by one shot, it forms supara-molecular hydrogen bond with receptor molecule; upon addition of the same by gradually, it shows F- induced chemical reaction, resulting in the formation of double additon product.

Dalton Transactions Accepted Manuscript

Published on 04 December 2013. Downloaded by St. Petersburg State University on 04/02/2014 19:50:25.

Graphical Abstract

Colorimetric detection of fluoride ion by 5-arylidenebarbituric acids: dual interaction mode for fluoride ion with single receptor.

Two 5-arylidenebarbituric acid derivatives (IH and IM) have been synthesized by the Knoevenagel condensation of barbituric acid with 4-N,N-dimethylami...
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