Ferrocene-based small molecules for dual-channel sensing of heavy- and transition-metal cations

The synthesis, electrochemical, optical, and cation-sensing properties of ferrocene-pentakis(phenylthio)benzene dyads, linked through a putative cation-binding 2-azadiene bridge, are presented. Dyad 5 behaves as a highly selective dual-redox and chromogenic chemosensor molecule for Pb(2+) cations; the oxidation redox peak is anodically shifted (DeltaE(1/2) = 125 mV), and the low energy band of the absorption spectrum is red-shifted (Delta lambda = 119 nm) upon complexation with this metal cation. Linear sweep voltammetry and spectroelectrochemical studies revealed that Cu(2+) and Hg(2+) metal cations induced oxidation of the ferrocene unit. The isomeric dyad 7, in which the nitrogen atom and the ferrocene unit are in closer proximity, has shown its ability for sensing both Pb(2+) and Hg(2+) ions; the oxidation redox peak is anodically higher shifted (DeltaE(1/2) = 340 mV), and the low energy band of the absorption spectrum is lower red-shifted (Delta lambda = 61 nm) that those found for dyad 5. The changes in the absorption spectra are accompanied by dramatic color changes which allow the potential for "naked eye" detection. A further exciting property of dyad 7 is that it behaves as an electrochemically induced switchable chemosensor for Pb(2+) and Hg(2+) because of the low metal-ion affinity of the oxidized 7(*+) species for these metal cations. The experimental data and conclusions about the ion-sensing properties are supported by DFT calculations.     

A highly selective redox, chromogenic, and fluorescent chemosensor for Hg2+ in aqueous solution based on ferrocene-glycine bioconjugates

The synthesis, electrochemical, optical, and metal-cation-sensing properties of ferrocene-glycine conjugates C(30)H(38)O(8)N(8)Fe (2) and C(20)H(24)O(4)N(4)Fe (3) have been documented. Both compounds 2 and 3 behave as very selective redox (ΔE(1/2) = 217 mV for 2 and ΔE(1/2) = 160 mV for 3), chromogenic, and fluorescent chemosensors for Hg(2+) cations in an aqueous environment. The considerable changes in their absorption spectra are accompanied by the appearance of a new low-energy peak at 630 nm (2, ε = 1600 M(-1) cm(-1); 3, ε = 822 M(-1) cm(-1)). This is also accompanied by a strong color change from yellow to purple, which allows a prospective for the "naked eye" detection of Hg(2+) cations. These chemosensors present immense brightness and fluorescence enhancement (chelation-enhanced fluorescence = 91 for 2 and 42 for 3) following Hg(2+) coordination within the limit of detection for Hg(2+) at 7.5 parts per billion.     

Cation coordination induced modulation of the anion sensing properties of a ferrocene-imidazophenanthroline dyad: multichannel recognition from phosphate-related to chloride anions

A new chemosensor molecule 1 based on a ferrocene-imidazophenanthroline dyad, effectively recognizes aqueous hydrogenpyrophosphate and the organic anions ADP and ATP through three different channels. A cathodic shift of the ferrocene/ferrocenium oxidation wave (Delta E 1/2 ranging from -130 mV for hydrogenpyrophosphate and fluoride to -40 mV for ADP). A progressive red-shift of the absorption bands and/or appearance of a new low energy band at 314-319 nm. These changes in the absorption spectra are accompanied by color changes from pale yellow to orange or pink, which allow the potential for "naked eye" detection. The emission spectrum (lambda exc = 390 nm) undergoes an important chelation-enhanced fluorescence effect (CHEF = 50) in the presence of 2.5 equiv of hydrogenpyrophosphate anion and with a large excess of fluoride anion (CHEF = 114). Interestingly, the emission spectrum obtained at different excitation energy (lambda exc = 340 nm) in the presence of AcOH acid is red-shifted and not only perturbed by the hydrogenpyrophosphate anion (CHEF = 71) but also with the organic anions ATP (CHEF = 25), ADP (CHEF = 15), and the dihydrogenphosphate (CHEF = 25). The stable heterobimetallic ruthenium (II) complex 2 selectively senses the chloride anion over other anions examined through two channels: cathodic redox shift (Delta E 1/2 = -80 mV) of the Fe(II)/Fe(III) redox couple keeping the oxidation wave of the ruthenium (II) center unchanged and a significant red emission enhancement (CHEF = 30). (1)H and (31)P NMR studies as well as DFT calculations have been carried out to get information about which molecular sites are involved in bonding. About the deprotonation/coordination dualism, the combined electrochemical, absorption, emission, and NMR data strongly support that fluoride anion induces only deprotonation, anions dihydrogenphosphate, ATP, and ADP from hydrogen-bonded complexes and formation of hydrogen-bonded complex between receptor 1 and hydrogenpyrophosphate anion and deprotonation proceed simultaneously. In regards to receptor 2, all available data (electrochemical, absorption, emission, and 1H NMR) strongly support the formation of a [2. Cl ( - ) ] hydrogen-bonded complex.     

Synthesis, structural charaterization, and electrochemical and optical properties of ferrocene-triazole-pyridine triads

The synthesis and electrochemical, optical, and cation-sensing properties of the ferrocene-triazole-pyridine triads 3 and 5 are presented. Azidoferrocene 1 and 1,1'-diazidoferrocene 4 underwent the "click" reaction with 2-ethynylpyridine to give the triads 3 and 5 in 81% and 68% yield, respectively. Electrochemical studies carried out in CH(3)CN in the presence of increasing amounts of Zn(2+), Ni(2+), Cd(2+), Hg(2+), and Pb(2+) metal cations, showed that the wave corresponding to the ferrocene/ferrocenium redox couple is anodically shifted by 70-130 mV for triad 3 and 167-214 mV for triad 5. The maximum shift of the ferrocene oxidation wave was found for 5 in the presence of Zn(2+). In addition, the low-energy band of the absorption spectra of 3 and 5 are red-shifted (Δλ = 5-10 nm) upon complexation with these metal cations. The crystal structures of compounds 3 and 5 and the complex [3(2)·Zn](2+) have been determined by single-crystal X-ray methods. (1)H NMR studies as well as density functional theory calculations have been carried out to get information about the binding sites that are involved in the complexation process.     

Highly selective mercury(II) cations detection in mixed-aqueous media by a ferrocene-based fluorescent receptor

A new chemosensor molecule 3 based on a ferrocene-imidazophenanthrophenazine dyad effectively recognizes Hg(2+) in an aqueous environment through three different channels. Upon recognition, an anodic shift of the ferrocene-ferrocenium oxidation potential (ΔE(1/2) = 240 mV) and a progressive red shift (Δλ = 17 nm) of the low energy band in its absorption spectrum is produced. The emission spectrum of 3 in an aqueous environment, CH(3)CN-EtOH-H(2)O (65:25:10), and conducted at pH = 7.4 (20 × 10(-3) M HEPES) (Φ = 0.003), is perturbed after addition of Hg(2+) cations and an intense and structureless red shift emission band at 494 nm (Δλ = 92 nm) appeared along with an increase of the intensity of the emission band (CHEF = 77), the quantum yield (Φ = 0.054) resulted in a 18-fold increase. The combined (1)H NMR data of the complex and the theoretical calculations suggest the proposed bridging coordination mode.     

Synthesis, electrochemical, and optical properties of linear homo- and heterometallocene triads

The synthesis, electrochemical, and optical properties of homo- (5, 8, 9, and 12) and heterometallic (6, 7, 10, and 11) ferrocene-ruthenocene triads, are presented. Triferrocenyl derivatives 5 and 9 form the mixed-valence species 5*+ and 92+ by partial oxidation, which show intramolecular electro-transfer phenomena. Interestingly, spectroelectrochemical studies of compound 11, bearing two peripheral ferrocene units and one central ruthenocene moiety, revealed the presence of low-energy bands in the near-infrared (NIR) region, which indicate a rather unusual intramolecular charge-transfer between the ferrocene and ruthenocene units. The value of the electronic coupling parameter V(ab) = 150 cm(-1) calculated by deconvolution of the observed Fe(II)-Fe(III) IVCT transition in the mixed-valence compound 11*+, (d(Fe(II)-Fe(III)) = 18.617 A), indicates the ability of the ruthenocene system to promote a long distance intervalence electron-transfer. Moreover, the reported triads show selective cation sensing properties. Triads 5, 9, and 11 behave as dual redox and optical chemosensors for Zn(2+), Hg(2+), and Pb(2+). Their oxidation redox peaks are anodically shifted (up to 130 mV), and their low-energy (LE) bands of the absorption spectra are red-shifted (up to 115 nm) upon complexation with these metal cations. These changes in the absorption spectra are accompanied by dramatic color changes which allow the potential for "naked eye" detection.     

Aldimines generated from aza-Wittig reaction between bis(iminophosphoranes) derived from 1,1'-diazidoferrocene and aromatic or heteroaromatic aldehydes: electrochemical and optical behaviour towards metal cations

Aldimine 4 bearing a 2-quinolyl group was prepared by aza-Wittig reaction between the triphenyliminophosphorane derived from the 1,1'-diazidoferrocene and 2-formylquinoline. However, aldimine 5, bearing a pyrene ring, was prepared using the most reactive tributyliminophosphorane derivative and the corresponding 1-formylpyrene. On the other hand, formation of aldimine 8 involves a tandem process, Staudinger reaction/intramolecular aza-Wittig reaction, by using directly 1,1'-diazidoferrocene and 2-(diphenylphosphonyl)benzaldehyde. Aldimine 4 behaves as chemosensor molecule for Ni(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+) cations through two different channels: electrochemical (ΔE(1/2) = 222-361 mV) and chromogenic (Δλ = 122-153 nm), which can be used for the "naked eye" detection of these metal cations. Aldimine 5 behaves as a highly selective redox (in CH(3)CN) and fluorescent (in CH(3)Cl-DMF) probe for Hg(2+) metal cations even in the presence of a large excess of the other metal cations tested. Aldimine 8 displays electrochemical affinity (ΔE(1/2) = 60-288 mV) to Li(+), Ca(2+), Mg(2+), Zn(2+) and Pb(2+) metal cations, with the phosphorus oxide functionality as a binding site. From the (1)H NMR titration data as well as DFT calculations, different tentative binding modes have been established, for these structurally related ferrocenyl derivatives.     

A simple but effective dual redox and fluorescent ion pair receptor based on a ferrocene-imidazopyrene dyad

The ferrocene-imidazopyrene dyad, bearing the imidazole ring as the only receptor site, acts as a redox and optical molecular sensor for ion pairs, exhibiting an easily detectable signal change in the redox potential of the ferrocene/ferrocinium redox couple and in the emission spectrum. Perturbation of the emission spectrum follows the order Pb(2+) > Hg(2+) > Zn(2+) for cations and H(2)PO(4)(-) > AcO(-) for anions.     

A bisferrocene-benzobisimidazole triad as a multichannel ditopic receptor for selective sensing of hydrogen sulfate and mercury ions

The bisferrocene-benzobisimidazole triad behaves as a selective redox and fluorescent chemosensor for HSO(4)(-) and Hg(2+) ions, exhibiting an easily detectable signal change in both the redox potential of the ferrocene/ferrocinium redox couple and in the emission band which is red-shifted (Δλ = 10-13 nm) and enhanced in intensity (Chelation Enhanced Fluorescence, CHEF = 486-225) upon complexation with these ions, in EtOH solutions.     

β‐Functionalized meso Tetrahalothien‐2‐ylporphyrins: Synthesis,Spectral, and Electrochemical Properties

Two types of β‐ functionalized (mono nitrated and perbrominated) meso tetrakis(5‐halothien‐;2‐yl)porphyrins, which can be used as precursors for the synthesis of other asymmetric and highly substituted porphyrins, have been synthesised and characterized. Introduction of a nitro group at the β‐ position shifted soret band 11–16 nm to the red region and redox potentials to > 170 mV for oxidation and > 250 mV for reduction anodically. Perbromination of halothienylporphyrins lead to enhanced bathochromically shifted uv‐visible spectral bands, but had only marginal influence on oxidation potentials. Effect of mono nitro group and eight bromo groups on the electronic properties of the porphyrins is attributed, respectively to, the electron deficiency created in the porphyrin π‐ system and the nonplanar conformation induced by the bulky bromo groups.     

Development and applications of fluorescent indicators for Mg2+ and Zn2+

In a study of the spectroscopic behavior of two Schiff base derivatives, salicylaldehyde salicylhydrazone (1) and salicylaldehyde benzoylhydrazone (2), Schiff base 1 has high selectivity for Zn(2+) ion not only in abiotic systems but also in living cells. The ion selectivity of 1 for Zn(2+) can be switched for Mg(2+) by swapping the solvent from ethanol-water to DMF (N,N-dimethylformamide)-water mixtures. Imine 2 is a good fluorescent probe for Zn(2+) in ethanol-water media. Many other ions tested, such as Li(+), Na(+), Al(3+), K(+), Ca(2+), Cr(3+), Mn(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Ag(+), Cd(2+), Sn(2+), Ba(2+), Hg(2+), and Pb(2+), failed to induce any spectral change in various solvents. The selectivity mechanism of 1 and 2 for metal ions is based on a combinational effect of proton transfer (ESPT), C═N isomerization, and chelation-enhanced fluorescence (CHEF). The coordination modes of the complexes were investigated.     

Dansyl-anthracene dyads for ratiometric fluorescence recognition of Cu2+

Dansyl-anthracene dyads 1 and 2 in CH(3)CN-H(2)O (7:3) selectively recognize Cu(2+) ions amongst alkali, alkaline earth and other heavy metal ions using both absorbance and fluorescence spectroscopy. In absorbance, the addition of Cu(2+) to the solution of dyads 1 or 2 results in appearance of broad absorption band from 200 nm to 725 nm for dyad 1 and from 200 nm to 520 nm for dyad 2. This is associated with color change from colorless to blue (for 1) and fluorescent green (for 2). This bathochromic shift of the spectrum could be assigned to internal charge transfer from sulfonamide nitrogen to anthracene moiety. In fluorescence, under similar conditions dyads 1 and 2 on addition of Cu(2+) selectively quench fluorescence due to dansyl moiety between 520-570 nm (for 1)/555-650 nm (for 2) with simultaneous fluorescence enhancement at 470 nm and 505 nm for dyads 1 and 2, respectively. Hence these dyads provide opportunity for ratiometric analysis of 1-50 μM Cu(2+). The other metal ions viz. Fe(3+), Co(2+), Ni(2+), Cd(2+), Zn(2+), Hg(2+), Ag(+), Pb(2+), Li(+), Na(+), K(+), Mg(2+), Ca(2+), Ba(2+) do not interfere in the estimation of Cu(2+) except Cr(3+) in case of dyad 1. The coordination of dimethylamino group of dansyl unit with Cu(2+) causes quenching of fluorescence due to dansyl moiety between 520-600 nm and also restricts the photoinduced electron transfer from dimethylamino to anthracene moiety to release fluorescence between 450-510 nm. This simultaneous quenching and release of fluorescence respectively due to dansyl and anthracene moieties emulates into Cu(2+) induced ratiometric change.     

A highly selective sulfur-free iridium(III)-complex-based phosphorescent chemidosimeter for detection of mercury(II) ions

A neutral phosphorescent coordination compound bearing a benzimidazole ligand, Ir(pbi)(2)(acac) (Hpbi = 1,2-diphenyl-1H-benzo[d]imidazole; Hacac = acetylacetone), is demonstrated to be the first example of a sulfur-free iridium complex for the detection of Hg(2+) cations with high selectivity and sensitivity. Ir(pbi)(2)(acac) shows a multisignaling response towards mercury(II) ions through UV-vis absorption, phosphorescence and electrochemistry measurements. Upon addition of Hg(2+) ions, solutions of this complex change from yellow to colorless, which could be observed easily by the naked eye, while its phosphorescence turns from bright green (λ(PLmax) = 520 nm) into faint skyblue (λ(PLmax) = 476 nm), and the detection limit is calculated to be 2.4 × 10(-7) mol L(-1). (1)H NMR spectroscopic titration as well as ESI-MS results indicate that the decomposition of Ir(pbi)(2)(acac) in the presence of Hg(2+) through rupture of Ir-O bonds is responsible for the significant variations in both optical and electrochemical signals.     

Synthesis and characterization of electroactive ferrocene derivatives: ferrocenylimidazoquinazoline as a multichannel chemosensor selectively for Hg2+ and Pb2+ ions in an aqueous environment

The synthesis and characterization of ferrocene (Fc) derivatives 4-[2,5-diferrocenyl-4-(4-pyridyl)imidazolidin-1-ylmethyl]pyridine (1), ferrocenylmethylenepyridin-3-ylmethylamine (2), N,N'-bis(ferrocenylmethylene)-2,4,6-trimethylbenzene-1,3-diamine (3), and 6-ferrocenyl-5,6-dihydro[4,5]imidazo[1,2-c]quinazoline (4) have been described. Structures of 1, 2, and 4 have been determined by single-crystal X-ray diffraction analyses. At 25 °C, 1-3 are nonfluorescent, while 4 displays moderate fluorescence and chromogenic, fluorogenic, and electrochemical sensing selectively toward Hg(2+) and Pb(2+) ions. Association constants (K(a)) for Hg(2+) and Pb(2+) have been determined by the Benesi-Hildebrand method. Job's plot analysis supported 1:1 and 1:2 stoichiometries for Hg(2+) and Pb(2+) ions. Cyclic voltammograms of 1-4 exhibited reversible waves corresponding to a ferrocene/ferrocenium couple. The wave associated with 4 (+0.0263 V) exhibited positive (ΔE(pa) = 0.136 V) and negative (ΔE(pa) = 0.025 V) shifts in the presence of Hg(2+) and Pb(2+) ions, respectively. The mode of interaction between metal ions and 4 has been supported by (1)H NMR spectroscopy and mass spectrometry studies and verified by theoretical studies. It presents the first report dealing with ferrocene-substituted quinazoline as a multichannel chemosensor for Hg(2+)/Pb(2+) ions.     

A highly selective fluorescent chemosensor for Pb2+

A new fluorescent sensor based on rhodamine B for Pb2+ was synthesized. The new fluorescent sensor showed an extreme selectivity for Pb2+ over other metal ions examined in acetonitrile. Upon the addition of Pb2+, an overall emission change of 100-fold was observed, and the selectivity was calculated to be 200 times that of Zn2+. The signal transduction occurs via of reversible CHEF (chelation-enhanced fluorescence) with this inherent quenching metal ion.     

Bis[1,1'-N,N'-(2-picolyl)aminomethyl]ferrocene as a redox sensor for transition metal ions

The compound bis[1,1'-N,N'-(2-picolyl)aminomethyl]ferrocene, L(1), was synthesized. The protonation constants of this ligand and the stability constants of its complexes with Ni(2+), Cu(2+), Zn(2+), Cd(2+) and Pb(2+) were determined in aqueous solution by potentiometric methods at 25 degrees C and at ionic strength 0.10 mol dm(-3) in KNO(3). The compound L(1) forms only 1:1 (M:L) complexes with Pb(2+) and Cd(2+) while with Ni(2+) and Cu(2+) species of 2 [ratio] 1 ratio were also found. The complexing behaviour of L(1) is regulated by the constraint imposed by the ferrocene in its backbone, leading to lower values of stability constants for complexes of the divalent first row transition metals when compared with related ligands. However, the differences in stability are smaller for the larger metal ions. The structure of the copper complex with L(1) was determined by single-crystal X-ray diffraction and shows that a species of 2:2 ratio is formed. The two copper centres display distorted octahedral geometries and are linked through the two L(1) bridges at a long distance of 8.781(10) Angstrom. The electrochemical behaviour of L(1) was studied in the presence of Ni(2+), Cu(2+), Zn(2+), Cd(2+) and Pb(2+), showing that upon complexation the ferrocene-ferrocenium half-wave potential shifts anodically in relation to that of the free ligand. The maximum electrochemical shift ([capital Delta]E(1/2)) of 268 mV was found in the presence of Pb(2+), followed by Cu(2+)(218 mV), Ni(2+)(152 mV), Zn(2+)(111 mV) and Cd(2+)(110 mV). Moreover, L(1) is able to electrochemically and selectively sense Cu(2+) in the presence of a large excess of the other transition metal cations studied.     

Heteroleptic dipyrrinato complexes containing 5-ferrocenyldipyrromethene and dithiocarbamates as coligands: selective chromogenic and redox probes

Six heteroleptic dipyrrinato complexes [Ni(fcdpm)(dedtc)] (1), [Ni(fcdpm)(dipdtc)] (2), [Ni(fcdpm)(dbdtc)] (3), [Pd(fcdpm)(dedtc)] (4), [Pd(fcdpm)(dipdtc)] (5), and [Pd(fcdpm)(dbdtc)] (6) (fcdpm = 5-ferrocenyldipyrromethene; dedtc = diethyldithiocarbamate; dipdtc = diisopropyldithiocarbamate; dbdtc = dibutyldithiocarbamate) have been synthesized and characterized by elemental analyses and spectral (ESI-MS, IR, (1)H, (13)C NMR, UV-vis) and electrochemical studies. Crystal structures of 1, 2, 4, and 5 have been authenticated by X-ray single-crystal analyses. Nickel-based complexes 1-3 display selective chromogenic and redox sensing for Hg(2+) and Pb(2+) ions, while palladium complexes 4-6 display selective chromogenic and redox sensing only for Hg(2+). Electronic absorption, ESI-MS, and electrochemical studies indicated that sensing arises from interaction between 1-3 and Hg(2+)/Pb(2+) through sulfur of the coordinated dithiocarbamates, while it arises from the pyrrolic nitrogen of fcdpm and dithiocarbamate sulfur from 4-6 and Hg(2+). Different modes of binding between Ni and Pd complexes have further been supported by theoretical studies. The receptor-cation binding constants (K(a)) and stoichiometry between probes and Hg(2+)/Pb(2+) have been estimated by the Benesi-Hildebrand method and Job's plot analysis. Detection limits for 1-3 toward Hg(2+)/Pb(2+) and 4-6 for Hg(2+) have been found to be reasonably high.     

A ferrocenyl-guanidine derivative as a highly selective electrochemical and colorimetric chemosensor molecule for acetate anions

A highly preorganized chemosensor molecule 1 based on a ferrocenyl-guanidine decorated with a chromogenic aryl azo moiety recognizes the acetate anion in acetonitrile solution. At first, receptor 1 underwent two-step oxidation events. Initially, oxidation of 1 occurs at the Fe(II) centre (E(p) = 440 mV) to form a ferrocenium species, followed by fast electron transfer from the guanidine moiety of the receptor to the Fe(III) centre with concomitant generation of an Fe(II) species with a radical cation centred at the nitrogen atom. In the second step, the radical cation species formed should undergo electrochemical oxidation at higher potential (E(p) = 830 mV). This assumption is supported by spectroelectrochemical studies. A remarkable cathodic shift (182 mV) of the ferrocene/ferrocenium oxidation peak (E(p) = 440 mV) and a progressive red-shift (Δλ = 30 nm) of the low energy band are observed in its absorption spectrum upon complexation of receptor 1 with the acetate anion. This change in the absorption spectrum is accompanied by a colour change from yellow to orange, which can be used for the "naked-eye" detection of this anion. Its monoprotonated form is able to selectively sense the less basic Cl(-), Br(-), NO(3)(-), and HSO(4)(-) anions: the oxidation redox peak at E(p) = 865 mV is cathodically shifted (107-182 mV).     

Peripheral metal-ion binding to tris(thia-oxo crown) porphyrazines

We report the preparation and solution properties of metal-free [1b(H(2))] and cobalt [1c(Co)] porphyrazines (pz's), where three pyrroles are functionalized with a S(2)O(3) crown ether for metal-ion binding and the fourth pyrrole is appended with two long-chain alcohols (bis((11-hydroxyundecyl)thio)) for potential use as surface anchors. Compounds 1b(H(2) and 1c(Co) exhibit ion-specific optical changes in the presence of Ag(+) and Hg(2+). Binding of Ag(+) to 1b(H(2)) is described by a 1:1 binding isotherm, with K(D) approximately 147 microM, whereas binding of Hg(2+) to 1b(H(2)) appears more complex. For 1c(Co), binding of Ag(+) and Hg(2+) also can be fit to a 1:1 isotherm, with K(D) approximately 109 and 83 microM, respectively. All four titrations show nonisosbesticity, including those apparently describable by the 1:1 isotherm, which indicates that there are intermediate stages as multiple ions bind. Neither 1b(H(2)) or 1c(Co) gives optical responses to Ni(2+), Zn(2+), Pb(2+), or Cu(2+) or to alkali (Li(+), Na(+), K(+), and Cs(+)) and alkaline earth (Mg(2+), Ca(2+), and Ba(2+)) metal ions. Nonetheless, "hard" ions are sensed electrochemically: Na(+) and Li(+) strongly shift the pz/pz(-) couple of 1b(H(2)()) and Co(III)/Co(II) couple of 1c(Co). For the addition of 4 equiv of Li(+) to 1c(Co), the Co(III)/Co(II) shifts +40 mV, and for the addition of 4 equiv of Na(+) to 1c(Co), the shift is +155 mV. The shifted redox waves of 1c(Co) all retain their reversibility. In contrast, for the addition of either 4 equiv of Li(+) or Na(+) to 1b(H(2)), the shifts of the pz/pz(-) couple are essentially the same, approximately 170 mV, and the shifted redox waves become broadened and less reversible, due to ion-induced aggregation. For 1c(Co) the shape of the titration curves [M]/[1b(H(2))] versus E(1/2) is concave to the x-axis, implying cooperative binding of multiple M(+) ions as part of the redox/binding system of equilibria.     

Multicolor fluorescence of a styrylquinoline dye tuned by metal cations

A styrylquinoline dye with a dipicolylamine (DPA) moiety (1) has been synthesized. The dye 1 in acetonitrile demonstrates multicolor fluorescence upon addition of different metal cations. Compound 1 shows a green fluorescence without cations. Coordination of 1 with Cd(2+) shows a blue emission, while with Hg(2+) and Pb(2+) exhibits yellow and orange emissions, respectively. The different fluorescence spectra are due to the change in intramolecular charge transfer (ICT) properties of 1 upon coordination with different cations. The DPA and quinoline moieties of 1 behave as the electron donor and acceptor units, respectively, and both units act as the coordination site for metal cations. Cd(2+) coordinates with the DPA unit. This reduces the donor ability of the unit and decreases the energy level of HOMO. This results in an increase in HOMO-LUMO gap and blue shifts the emission. Hg(2+) or Pb(2+) coordinate with both DPA and quinoline units. The coordination with the quinoline unit decreases the energy level of LUMO. This results in a decrease in HOMO-LUMO gap and red shifts the emission. Addition of two different metal cations successfully creates intermediate colors; in particular, the addition of Cd(2+) and Pb(2+) at once creates a bright white fluorescence.