Host-guest complexation of a fluorescent and electrochemical chemsensor for fluoride anion

Host-guest complexation of a ferrocenenylphalene dyad 1, 1,1'-diaceylferrocenyl-3-hydroxyl-2-naphthoylhydrazone, as a fluorescent and electrochemical chemosensor for fluoride anion, was investigated. Crystal structure analysis revealed that the two naphthyl arms of compound 1 positioned in the same side about the ferrocene moiety and interacted through pi-pi stacking interactions. The intermolecular pi-pi stacking interactions and the C-H...pi interactions between the ferrocene moieties and the naphthalene rings linked the molecules together featuring a two-dimensional layered structure. Fluorescence titrations of compound 1 indicated that in the presence of F- and H2PO4-, the emission intensities enhanced significantly. Electrochemical titrations revealed that compound 1 sensed the F- anion in high selectivity with a cathodic shift of 120 mV, and had no sense in recognizing H2PO4- anion. 1H NMR titrations demonstrated that while compound 1 hydrogen-bonded to H2PO4- forming simple 1 : 1 host-guest complex, further addition of F- induced the deprotonation of compound 1.     

Lanthanide/ATP interaction in water mediated by luminescent hemispherical-shaped complexes

Ligand LH(2), composed of two bipyridylcarboxylate fragments linked to an amino butyl chain, reacts with europium and terbium to form luminescent complexes in water at neutral pH. When testing these unsaturated complexes as anion sensors with NO(3)(-), HPO(4)(2)(-), AMP, ADP, and ATP, a marked selectivity is observed for HPO(4)(2)(-) and ATP(4)(-) at pH = 7.0. The interaction of these anions with the complex was investigated by means of absorption and emission spectroscopies. With ATP(4)(-), ES-MS and (31)P NMR experiments revealed the formation of a [Ln.L.(ATP)](3)(-) ternary species.     

Ferrocene-based heteroditopic receptors displaying high selectivity toward lead and mercury metal cations through different channels

The synthesis and electrochemical, optical, and ion-sensing properties of ferrocene-imidazophenazine dyads are presented. Dyad 4 behaves as a highly selective chemosensor molecule for Pb(2+) cations in CH(3)-CN/H(2)O (9:1). The emission spectrum (λ(exc) = 317 nm) undergoes an important chelation-enhanced fluorescence effect (CHEF = 47) in the presence of Pb(2+) cations, a new low-energy band appeared at 502 nm, in its UV/vis spectrun, and the oxidation redox peak is anodically shifted (ΔE(1/2) = 230 mV). The presence of Hg(2+) cations also induced a perturbation of the redox potencial although in less extension than those found with Pb(2+) cations. Dyad 7, bearing two fused pyridine rings, has shown its ability for sensing Hg(2+) cations selectively through three channels: electrochemical, optical, and fluorescent; the oxidation redox peak is anodically shifted (ΔE(1/2) = 200 mV), a new low-energy band of the absorption spectrum appeared at 485 nm, and the emission spectrum (λ(exc) = 340 nm) is red-shifted by 32 nm accompanied by a remarkable chelation-enhanced fluorescent effect (CHEF = 165). Linear sweep voltammetry revealed that Cu(2+) cations induced oxidation of the ferrocene unit in both dyads. (1)H NMR studies have been carried out to obtain information about the molecular sites which are involved in the binding process.     

Macrocyclic Eu3+ chelates show selective luminescence responses to anions

A series of lanthanide-containing macrocycles, Eu2-Eu5, exhibited unique luminescent responses in the presence of strong hydrogen-bond-accepting anions (F-, CH3COO-, and H2PO4-) in dimethyl sulfoxide. The macrocycles examined herein were designed to include a lanthanide chelate, aromatic spacers that function as antennae, thiourea groups as anion-binding units, and an alkyl or aryl linker between the thioureas that tailors the size and rigidity of the macrocycle. The anion-induced change in the emission intensity (lambda(exc) = 272 nm; lambda(em) = 614 nm) varied across the series of macrocycles and was dependent on the basicity of the anion. The largest luminescence response was observed in Eu(2), whereby the emission increased 77% upon the addition of 8 equiv of fluoride. A change in luminescence was not observed when exciting Eu3+ directly (lambda(exc) = 395 nm) over the course of anion titration experiments with all of the anions studied. These macrocycles contain only slight variations in structure, and insights into the mechanism of the anion interaction have been gained through monitoring of anion titrations via luminescence, absorbance, and luminescence lifetime measurements. In addition, model compounds (2-5) lacking the Eu3+ moiety were synthesized to study the binding pockets of Eu2-Eu5 using absorbance and 1H NMR spectroscopy. These studies indicate that the anions interact with the thiourea moiety of Eu2-Eu5, and the luminescent response is controlled by changes in the morphology of the macrocycle binding pocket.     

Anion-induced urea deprotonation

The urea-based receptor 1 (1-(7-nitrobenzo[1,2,5]oxadiazol-4-yl)-3-(4-nitrophenyl)urea, L--H), interacts with X- ions in MeCN, according to two consecutive steps: 1) formation of a hydrogen-bond complex [L--H...X]-; 2) deprotonation of L--H to give L- and [HX2]-, as shown by spectrophotometric and 1H NMR titration experiments. Step 2) takes place with more basic anions (fluoride, carboxylates, dihydrogenphosphate), while less basic anions (Cl-, NO2-, NO3-) do not induce proton transfer. On crystallisation from a solution containing L--H and excess Bu4NF, the tetrabutylammonium salt of the deprotonated urea derivative (Bu4N[L]) was isolated and its crystal and molecular structure determined.     

Labile zinc-assisted biological phosphate chemosensing and related molecular logic gating interpretations

Herein, molecular fluorescence 'OFF-ON' behavior with aqueous addition of biological phosphate and Zn(2+) is studied with Zn(2)(slys)(2)Cl(2) [H(2)slys = 6-amino-2-{(2-hydroxybenzylidene)amino}hexanoic acid], a fluorescent water-soluble complex, using various spectroscopic tools (e.g., (31)P NMR, UV-vis, emission, and CD spectroscopy) at the micromolar level. Adduct-dependent fluorescence intensity changes can be interpreted as a two-input (cation/anion) implication molecular logic gating system. A displacement study of PPi from the dizinc complex is also reported. Diphosphate and triphosphate addition/displacements were also studied. (31)P NMR spectroscopy shows gradual NMR peak shifts from bound ADP/GDP to free ADP/GDP with increasing [PPi]. In the emission spectrum, fluorescence quenching is shown: CD signal maxima decrease with addition of PPi. These displacement events are also tested with triphosphates (ATP, GTP), and their binding strength/displacement ability over ADP/GDP is quantified: PPi > ATP ≈ GTP (3.35 ± 0.77 × 10(4) M(-1) for PPi, 7.73 ± 1.79 × 10(3) M(-1) for ATP, 9.21 ± 2.88 × 10(3) M(-1) for GTP over 1·ADP). Many anions and cations were also screened for selectivity. Tubulin polymerization was assayed in the presence of 1 and its copper analogue which reflected a slight inhibition in polymerization.     

Detailing hydrogen bonding and deprotonation equilibria between anions and urea/thiourea derivatives

Spectrophotometric and 1H NMR titrations of N-methoxyethyl-N'-(4-nitrophenyl)thiourea (3) by Bu(4-)NOAc show that in DMSO deprotonation of the receptor and formation of a hydrogen-bonded complex with anion proceed simultaneously but in MeCN deprotonation requires the participation of the second acetate anion. The formation constants of hydrogen-bonded complexes were determined from titrations in the presence of added acetic acid, which suppressed deprotonation. These constants together with independently measured stability constants of (AcO)(2)H(-) complexes were employed for a rigorous numerical analysis of titration results in the absence of added acid, which allowed us to determine the equilibrium deprotonation constants as well as pKa values for 3 in both solvents. Although 3 appeared to be a weaker acid than AcOH in both solvents, it can be deprotonated by acetate in dilute solutions when the concentration of liberated acetic acid is low enough. With disubstituted N,N-bis(methoxyethyl)-N'-(4-nitrophenyl)thiourea 4 only deprotonation equilibrium is observed. In contrast, both parent urea derivatives 1 and 2 cannot be deprotonated by acetate anions. Independent of the real type of equilibrium, whether it is a deprotonation or a hydrogen bonding, titration plots always can be satisfactorily fitted to a formal 1:1 binding isotherm. A relationship between apparent "binding constants" and real equilibrium constants of hydrogen bonding association and deprotonation processes is discussed.     

Photophysical and anion sensing properties of platinum(II) terpyridyl complexes with phenolic ethynyl ligands

A series of platinum(ii) terpyridyl complexes with phenolic ethynyl ligands have been synthesized and characterized. Their photophysical and sensing properties towards anions such as fluoride, acetate and dihydrogenphosphate have been investigated. These complexes show a colorimetric response and fluorescence quenching in the presence of anions including fluoride, acetate and dihydrogenphosphate, and selective sensing towards fluoride in some cases. The sensing mechanism has been investigated by spectrophotometric and (1)H NMR titration.     

Imidazolium-based macrocycles as multisignaling chemosensors for anions

A series of structurally novel anion receptors , , and in which a ferrocene unit and a fluorescent moiety are linked to two imidazolium rings have been designed and prepared from 1,1'-bis(imidazolylmethyl)ferrocene. Their crystal structures revealed that these receptors are capable of incorporating anions such as PF(6)(-) and Br(-). Consequently, the anion binding studies were carried out using various techniques including electrochemistry (CV and OSWV), fluorescence, UV-vis, and (1)H NMR spectroscopy. All the receptors showed a special electrochemical response to the F(-) anion with a remarkable cathodic shift of more than 260 mV and displayed a unique selectivity for F(-) and AcO(-) anions with fluorescence enhancement over various other anions of present interest (Cl(-), Br(-), I(-), HSO(4)(-), H(2)PO(4)(-)). In addition, for receptor , obvious absorption changes were observed when the H(2)PO(4)(-) anion was added while other anions (F(-), Cl(-), Br(-), I(-), AcO(-), HSO(4)(-)) showed only a minor influence on the UV-vis spectra. (1)H NMR titrations demonstrated that receptors and can bind anions through (C-H)(+)X(-) hydrogen bonds and showed strong affinity and high selectivity for the AcO(-) anion in acetonitrile.     

Urea-based ruthenium(II)-polypyridyl complex as an optical sensor for anions: synthesis, characterization, and binding studies

A new ruthenium(II) complex [Ru(bpy)2(1-(6-nitro-[1,10]phenanthrolin-5-yl)-3-(4-nitrophenyl)-urea)] (bpy=2,2'-bipyridyl) was synthesized and characterized using standard analytical and spectroscopic techniques. Detailed absorption, emission, and 1H NMR spectral studies revealed that this receptor molecule acts as a sensor for F-, CH3COO-, and H2PO4- in acetonitrile solution. Binding of these anions caused an appreciable change in the color of the acetonitrile solution, which could be detected with the naked eye. At relatively lower concentration of anions, 1:1 H-bonded adduct was formed; however, at higher concentration, classical Br?nsted acid-base-type reaction prevailed. The relative binding affinity of different anions toward this receptor was evaluated and was rationalized with quantum chemical calculations. Narrowing of the gap between the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels on deprotonation of the receptor molecule caused a faster decay of the luminescence lifetime for the Rudpi-->Lpi*/bpypi*-based triplet excited state.     

Synthesis, structural characterization, and photophysical, electrochemical, intercomponent energy-transfer, and anion-sensing studies of imidazole 4,5-bis(benzimidazole)-bridged Os(II)Os(II) and Ru(II)Os(II) bipyridine complexes

Homo- and heterobimetallic complexes of composition [(bpy)(2)M(II)(H(2)Imbzim)M'(II)(bpy)(2)](ClO(4))(3)·nH(2)O, where M(II) = M'(II) = Os (1), M(II) = Ru and M'(II) = Os (2), H(3)Imbzim = 4,5-bis(benzimidazole-2-yl)imidazole, and bpy = 2,2'-bipyridine, have been synthesized and characterized using standard analytical and spectroscopic techniques. Both of the complexes crystallized in monoclinic form with the space group P2(1)/m for 1 and P2(1)/n for 2. The absorption spectra, redox behavior, and luminescence properties of the complexes have been thoroughly investigated. The complexes display very intense, ligand-centered absorption bands in the UV region and moderately intense metal-to-ligand charge-transfer (MLCT) bands in the visible region. The bimetallic complexes show two successive one-electron reversible metal-centered oxidations. The strong fluorescence of free H(3)Imbzim is completely quenched in the metal complexes by energy transfer to the metal-based units, which exhibit their characteristic MLCT phosphorescence. The luminescence data of the heterometallic complex 2 show that electronic energy transfer takes place from the ruthenium center to the osmium-based component. The anion binding properties of the complexes have been studied in solutions using absorption, emission, and (1)H NMR spectral measurements. The metalloreceptors act as sensors for F(-) and AcO(-) ions. Sensing studies indicate the presence of two successive anion-induced deprotonation steps, leading to the formation of [(bpy)(2)M(HImbzim)M'(bpy)(2)](2+) and [(bpy)(2)M(Imbzim)M'(bpy)(2)](+) species. Double deprotonation is also observed in the presence of hydroxide. The binding affinities of different anions toward the receptors have been evaluated. Cyclic voltammetry measurements carried out in acetonitrile have provided evidence in favor of anion-dependent electrochemical responses of the bimetallic metalloreceptors with F(-) and AcO(-) ions.     

A fluorescent chemosensor for fluoride anions based on a hemicyanine dye

A hemicyanine dye with imidazole as the acceptor was designed and prepared as a chemosensor for fluoride anions. The experimental results demonstrated that it is a fluorometric probe for fluoride anion with good sensitivity and high selectivity. This probe showed obvious changes in UV–Vis absorption and fluorescence spectra in the presence of fluoride anions, which are attributed to the deprotonation of N–H on the imidazole moiety with fluoride anions.     

Novel Chromogenic Chemosensors for Fluoride Anion Based on 8-Hydroxyquinoline Azo Derivatives

A series of 8-hydroxyquinoline azo derivatives with diverse conjugated structures were synthesized and studied to chromogenicaUy detect anions. All the dyes allowed selective detection for fluoride anion in CH3CN via instant deprotonation of the compounds, which was affirmed by UV-Vis absorption and 1H NMR spectra. The chromogenically responding ability increases as the substituent changes from phenyl to naphthyl or anthryl. This result is likely to be related to the enhancement of intramolecular charge transfer （ICT） induced by extension of conjugated structure.     

两种结构简单绕丹宁衍生物的合成及其对氟离子的选择性识别研究

设计合成了两个结构简单的绕丹宁衍生物,在CH₂Cl₂-DMSO混合溶剂中利用紫外-可见吸收光谱研究了其与多种阴离子的相互作用,发现它们的吸收光谱对氟离子呈现特异性变化,吸收滴定实验确认它们与氟离子间相互作用的化学计量比为1:1,¹H NMR进一步证实它们与氟离子的作用类型为氢键或脱质子作用。     

Neutral acyclic anion receptor with thiadiazole spacer: halide binding study and halide-directed self-assembly in the solid state

A halide binding study of a newly synthesized neutral acyclic receptor LH(2) with a thiadiazole spacer has been methodically performed both in solution and in the solid state. Crystal structure analysis of the halide complexes elucidate the fact that fluoride forms an unusual 1:1 hyrogen-bonded complex with monodeprotonated receptor, whereas in the case of other congeners, such as chloride and bromide, the receptor binds two halide anions along with formation of a halide-bridged 1D polymeric chain network by participation of N-H···X(-) and aromatic C-H···X(-) hydrogen-bonding (where X = Cl and Br) interactions. The presence of a rigid thiadiazole spacer presumably opens up enough space for capturing two halide anions by a single receptor molecule, where the coordinated -NH protons are pointed in the same direction with respect to the spacer and eventually favor formation of halide (Cl(-) and Br(-)) induced polymeric architecture, although no obvious chloride- or bromide-directed polymeric assembly is found in solution. A significant red shift of 243 nm in the absorption spectra of LH(2) was solely observed in the presence of excess fluoride anion, which enables LH(2) as an efficient colorimetric sensor for optical detection of fluoride anion (yellow to blue). Furthermore, spectroscopic titration experiments with increasing equivalents of fluoride anion suggest formation of a H-bonded complex with subsequent stepwise deprotonation of two N-H groups, which can be visually monitored by a change in color from yellow to blue via pink.     

Colorimetric sensing of anions in aqueous solution using a charge neutral, cleft-like, amidothiourea receptor: tilting the balance between hydrogen bonding and deprotonation in anion recognition

The design, synthesis and physical evaluation of 1, a visible colorimetric 'naked eye' pyridyl based bis-amidothiourea sensor for anions, is described. This charge neutral sensor gives rise to significant changes in the absorption spectra upon interactions with several important biological anions such as AMP and ADP in 4:1 DMSO-H(2)O solution, while ATP was not detected. These colorimetric changes are due to the formation, or the combination of hydrogen bonding complexes and/or deprotonation between these anions and 1.     

Synthesis, structural characterization, photophysical, electrochemical, and anion-sensing studies of luminescent homo- and heteroleptic ruthenium(II) and osmium(II) complexes based on terpyridyl-imidazole ligand

A series of hetero- and homoleptic tridentate ruthenium(II) and osmium(II) complexes of compositions [(tpy-PhCH(3))Ru(tpy-HImzphen)](ClO(4))(2) (1), [(H(2)pbbzim)Ru(tpy-HImzphen)](ClO(4))(2) (2), and [M(tpy-HImzphen)(2)](ClO(4))(2) [M = Ru(II) (3) and Os(II) (4)], where tpy-PhCH(3) = 4'-(4-methylphenyl)-2,2':6',2"-terpyridine, H(2)pbbzim = 2,6-bis(benzimidazole-2-yl)pyridine and tpy-HImzphen = 2-(4-[2,2':6',2"]terpyridine-4'-yl-phenyl)-1H-phenanthro[9,10-d]imidazole, have been synthesized and characterized by using standard analytical and spectroscopic techniques. X-ray crystal structures of three complexes 2, 3, and 4 have been determined. The absorption spectra, redox behavior, and luminescence properties of the complexes have been thoroughly investigated. All of the complexes display moderately strong luminescence at room temperature with lifetimes in the range of 10-55 ns. The effect of solvents on the absorption and emission spectral behavior of the complexes has also been studied in detail. The anion sensing properties of all the complexes have been studied in solution using absorption, emission, and (1)H NMR spectral studies and by cyclic voltammetric (CV) measurements. It has been observed that the complexes 1, 3, and 4 act as sensors for F(-)only, whereas 2 acts as sensor for F(-), AcO(-), and to some extent for H(2)PO(4)(-). It is evident that in the presence of excess of anions deprotonation of the imidazole N-H fragment(s) occurs in all cases, an event which is signaled by the development of vivid colors visible with the naked eye. The receptor-anion binding/equilibrium constants have been evaluated.     

Novel indole based colorimetric and "turn on" fluorescent sensors for biologically important fluoride anion sensing

A novel indole Hydrazone receptor 1 has been synthesized by one step of condensation, which can act as an efficient colorimetric and "turn on" fluorescent sensor for fluoride anions; Benesi-Hildebrand equation indicates that 1 associates with F(-) in a 1:1 stoichiometry; [TBA]OH and (1)H NMR titration experiments indicate that the deprotonation process involved upon addition of fluoride anions.     

Synthesis and evaluation of thiosemicarbazones functionalized with furyl moieties as new chemosensors for anion recognition

A family of heterocyclic thiosemicarbazone dyes ( and ) containing furyl groups was synthesized in good yields, characterized and their response in acetonitrile in the presence of selected anions was studied. Acetonitrile solutions of and showed absorption bands in the 335-396 nm range which are modulated by the electron donor or acceptor strength of the heterocyclic systems appended to the thiosemicarbazone moiety. Fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulphate, nitrate, acetate and cyanide anions were used in recognition studies. From these anions, only sensing features were seen for fluoride, cyanide, acetate and dihydrogen phosphate. Two clearly different chromo-fluorogenic behaviours were observed: (i) a small shift of the absorption band due to the coordination of the anions with the thiourea protons and (ii) the appearance of a new red shifted band due to deprotonation. For the latter effect, a change in the colour of solution from pale yellow to purple was observed. Fluorescence studies were also in agreement with the different effects observed in the UV/Vis titrations. In this case, hydrogen bonding interactions were visible through the enhancement of the emission band, whereas deprotonation induced the appearance of a new red-shifted emission. Logarithms of stability constants for the two processes (complex formation + deprotonation) for receptors in the presence of fluoride and acetate anions were determined from spectrophotometric titrations using the HypSpec V1.1.18 program. Semi-empirical calculations to evaluate the hydrogen-donating ability of the receptors and a prospective electrochemical characterization of compound in the presence of fluoride were also performed.     

Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazones

A family of heterocyclic thiosemicarbazone dyes (3a–d) containing thienyl groups has been synthesized, characterized, and their chromo-fluorogenic response in acetonitrile in the presence of selected anions was studied. Acetonitrile solutions of 3a–d show absorption bands in the 338–425 nm range, which are modulated by the groups attached to the thiosemicarbazone moiety. The fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulfate, nitrate, acetate, and cyanide anions were used in the recognition studies. Only sensing features were observed for fluoride, cyanide, acetate, and dihydrogen phosphate anions. Two different chromogenic responses were found, (i) a small shift of the absorption band due to coordination of the anions with the thiourea protons and (ii) the appearance of a new red-shifted band due to deprotonation of the receptor. For the latter process changes in the color solutions from pale-yellow to orange-red were observed. Fluorescence studies showed a different emission behavior according to the number of thienyl rings in the π-conjugated bridges. Stability constants for the two processes (complex formation+deprotonation) for receptors 3a–d in the presence of fluoride and acetate anions were determined from spectrophotometric titrations using the HypSpec program. The interaction of 3d with fluoride was studied through ¹H NMR titrations. Semiempirical calculations to evaluate the hydrogen-donating ability of the receptors were also performed.