Chelation-enhanced Fluorescence Effect Research Articles

Metal ion selectivities of the highly preorganized tetradentate ligand 1,10-phenanthroline-2,9-dicarboxamide with lanthanide(III) ions and some actinide ions

Abstract Metal ion complexing properties of the ligand PDAM (1,10-phenanthroline-2,9-dicarboxamide) are reported in relation to its possible use as a functional group for solvent extractants in the separation of Am(III) from Ln(III) (lanthanide) ions. PDAM is only slightly water soluble, but variation of the intense π–π* transitions in the UV spectrum of 2×10−5 M PDAM solutions as a function of pH or metal ion concentration allowed for the determination of the protonation constant (pK) and logK 1 values with metal ions. The pK of PDAM is 0.6±0.1 in 1.0 M NaClO4, the lowest for any 1,10-phenanthroline (phen) derivative (in contrast, pK phen=5.1), which is attributed to the electron-withdrawing properties of the amide substituents of PDAM. The weak proton basicity of PDAM may be an important factor in its use as the functional group of a solvent extractant from acidic solutions. The formation constants are determined by UV-Visible spectroscopy for the Ln(III) ions from La(III) to Lu(III) (excluding Pm(III)), as well as for Y(III), Sc(III), Th(IV), and the UO2 2+ cation in 0.1 M NaClO4 at 25 °C. The logK 1 values for the Ln(III) ions show only small changes from La(III) to Lu(III) (both have logK 1 = 3.80). The amide O-donors (oxygen donors) of the amide groups of PDAM appear to cause considerable stabilization of the complexes of PDAM as compared to those of phen, consistent with the idea that the neutral O-donor is a strong Lewis base towards large metal ions such as the Ln(III) ions. A reviewer has pointed out that the amide groups would also stabilize the complexes of PDAM by virtue of the chelate effect, in that PDAM is tetradentate, while phen is only bidentate. The small change in complex stability for PDAM complexes in passing from La(III) to Lu(III) is rationalized in terms of the idea that neutral O-donors stabilize the complexes of the large La(III) ion more than the smaller Lu(III) ion, offsetting the greater affinity of Lu(III) than La(III) for N-donor ligands. The complexes of Th(IV), Sc(III), and the UO2 2+ cation with PDAM have logK 1 values slightly higher than those of the Ln(III) cations, while Y(III) forms a slightly less stable complex. The best-fit size of metal ion for coordination with PDAM is analyzed using molecular mechanics calculations. A fluorescence study shows that the free ligand PDAM fluoresces very strongly, but that the Ln(III) cations quench the fluorescence of PDAM rather than produce a chelation enhanced fluorescence (CHEF) effect as Ln(III) ions do with other phen-based tetradentate ligands. Possible reasons for the lack of a CHEF effect with PDAM are discussed.

Effect of bis‐triazoles on a ribose‐based fluorescent sensor

We synthesized two ribosyl-based fluorescent sensors. Both sensors have an anthracene as the fluorophore, but they differ in the recognition site for metal ions. One (3) has two ribosyl esters, and the other (6) has two triazole groups linked to two ribosyl esters. Among the metal ions examined in MeOH, compound 3 displayed a large chelation-enhanced fluorescence (CHEF) effect with Hg(2+) and Cu(2+) ions, and compound 6 displayed a large chelation-quenched fluorescence (CHQF) effect with Cu(2+) and Ni(2+) ions. The results demonstrated that the absence (sensor 3) and presence (sensor 6) of an incorporated bis-triazole group in a ribosyl-based fluorescent sensor conferred different preferences and distinct binding modes for metal ions.

A novel small molecule fluorescent sensor for Zn2+ based on pyridine–pyridone scaffold

The development of a water-soluble and small molecular weight fluorescent probe, 3-(4-methoxyphenyl)-4-(methylsulfanyl)-6-(pyridin-2-yl)pyridin-2(1H)-one (3), for detecting Zn2+ based on pyridine–pyridone skeleton is reported. We observed a clear chelation enhanced fluorescence effect of 3 in the presence of Zn2+. Other fluorescent properties of 3 are discussed.

A FRET fluorescent chemosensor SPAQ for Zn2+ based on a dyad bearing spiropyran and 8-aminoquinoline unit

A novel FRET fluorescent sensor SPAQ containing 8-aminoquinoline (donor) and spiropyran derivative (acceptor) was designed and synthesized for detecting Zn2+. The probe successfully exhibited a fluorescence turn on and ratiometric response for Zn2+ in ethanol solution with high selectivity. Upon excitation at 370 nm, the modulation of the emission intensity of SPAQ at 645 and 470 nm was achieved in the presence of Zn2+ by fluorescent resonance energy transfer (FRET) and chelation-enhanced fluorescence (CHEF) effects.

A multifaceted ferrocene-benzobisimidazole derivative: fluorogenic probe for Pb2+ and Zn2+ cations and unconventional fluorescence behaviour towards Cu2+ metal cations

The ferrocene-benzobisimidazole derivative shows high affinity for Pb(2+) and Zn(2+) metal cations over a range of other metal cations examined. In the presence of Pb(2+) the emission spectrum is red-shifted by 13 nm with an important chelation-enhanced fluorescence effect (CHEF) CHEF = 55. The presence of Zn(2+) cations also induced a perturbation of the emission spectrum although to a lesser extent than that found for Pb(2+) cations (CHEF = 37). Upon complexation with Cu(2+) cations, not only is the emission band red-shifted (Deltalambda = 67 nm) with a noticeable CHEF = 20, but also the maximum of such fluorescence emission exhibits a concomitant shift towards higher wavelengths when the excitation wavelength is gradually shifted to the red-edge of the absorption band (red-edge effect).

Complexation of Metal Ions of Higher Charge by the Highly Preorganized Tetradentate Ligand 2,9-Bis(hydroxymethyl)-1,10-Phenanthroline. A Crystallographic and Thermodynamic Study

The metal ion selectivity for M(III) (M = metal) ions exhibited by the highly preorganized ligand PDALC is investigated (PDALC = 2,9-bis(hydroxymethyl)-1,10-phenanthroline). The structures are reported of [Bi(PDALC)(H(2)O)(2)(ClO(4))(3)] x H(2)O (1), monoclinic, P2(1)/c, a = 12.8140(17), b = 19.242(3), c = 9.2917(12) A, beta = 91.763(2) degrees, V = 2289.9(5) A(3), Z = 4, R = 0.0428; [Th(PDALC)(NO(3))(4)] x 3 H(2)O (2), monoclinic, P2(1)/n, a = 7.876(3), b = 22.827(9), c = 12.324(5) A, beta = 94.651(6) degrees, V = 2208.4(15) A(3), Z = 4, R = 0.0669; [Cd(PDALC)(2)](ClO(4))(2) (3)), triclinic, P1, a = 7.5871(16), b = 13.884(3), c = 14.618(3) A, alpha = 74.081(2) degrees, beta = 88.422(2) degrees, gamma = 78.454(2) degrees, V = 1450.2(5) A(3), Z = 2, R = 0.0267. The Bi in 1 is best regarded as 9-coordinate, with four short bonds to the PDALC, and two short bonds to the coordinated water molecules, with three long bonds to perchlorate oxygens. The Bi-N bonds at 2.35 A are by a considerable margin the shortest Bi-N bonds to 1,10-phenanthroline (phen) type ligands, which is suggested to be due to the Bi adapting to the metal ion size requirements of PDALC. The Th(IV) in 2 is 12-coordinate, with four bonds to PDALC, and the four chelated nitrates, with close to normal bond lengths to the PDALC ligand. The Cd(II) in 3 is 8-coordinate, with Cd-N and Cd-O bonds that are similar to those found in other 8-coordinate Cd(II) complexes. The five known structures of PDALC complexes, including the three reported here, suggest that the M-N bonds to PDALC are quite easily varied in length in response to differing metal ion sizes, but that the M-O bonds are more constrained by the rigid ligand to be close to the ideal value of 2.50 A. The formation constants (log K(1)) for M(III) ions with PDALC show that for small metal ions such as Ga(III) and Fe(III), log K(1) is only slightly higher than for phen, suggesting that these metal ions are too small to coordinate to the alcoholic oxygen donors of PDALC. For larger metal ions such as Bi(III), Gd(III), Th(IV), and UO(2)(2+), log K(1) for PDALC is higher than log K(1) for phen by more than 5 log units, which stabilization is attributed to the fact that PDALC is preorganized for complexation with large metal ions with an ionic radius of about 1.0 A. The fluorescence of M(III) complexes of PDALC is discussed. PDALC free ligand gives fluorescence typical of phen ligands, with the protonated form giving a broad less intense band, and the non-protonated form of the ligand giving an intense structured set of bands. Large lanthanide ions without partially filled f-subshells, such as La(III), Lu(III), and also Y(III), give a fairly strong CHEF (chelation-enhanced fluorescence) effect, while those with partially filled f-subshells, such as Gd(III), Yb(III), and Tb(III), strongly quench the fluorescence of PDALC. A heavy element such as Bi(III) has strong spin-orbit coupling effects that act to quench the fluorescence of PDALC almost completely, which effect is enhanced by the covalence of the Bi-N bonds.

Strong Metal Ion Size Based Selectivity of the Highly Preorganized Ligand PDA (1,10-Phenanthroline-2,9-dicarboxylic Acid) with Trivalent Metal Ions. A Crystallographic, Fluorometric, and Thermodynamic Study

The selectivity of the rigid ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) for some M(III) (M = metal) ions is presented. The structure of [Fe(PDA(H)(1/2))(H(2)O)(3)] (ClO(4))(2).3H(2)O.(1)/(2)H(5)O(2) (1) is reported: triclinic, P1, a = 7.9022(16) A, b = 12.389(3) A, c = 13.031(3) A, alpha = 82.55(3) degrees , beta = 88.41(3) degrees , gamma = 78.27(3) degrees , V = 1238.6(4) A(3), Z = 2, R = 0.0489. The coordination geometry around the Fe(III) is close to a regular pentagonal bipyramid, with Fe-N lengths averaging 2.20 A, which is normal for a 1,10-phenanthroline type of ligand coordinated to seven-coordinate Fe(III). The Fe-O bonds to the carboxylate oxygens average 2.157 A, which is rather long compared to the average Fe-O length of 2.035 A to carboxylates in seven-coordinate Fe(III) complexes. The structure of 1 supports the idea that the Fe(III) is too small for ideal coordination in the cleft of PDA, and the structure shows that the Fe(III) adapts to this by inducing numerous small distortions in the structure of the PDA ligand. The log K(1) values for PDA at 25 degrees C in 0.1 M NaClO(4) were determined by UV spectroscopy with Al(III) (log K(1) = 6.9), Ga(III) (log K(1) = 9.7), In(III) (log K(1) = 19.7), Fe(III) (log K(1) = 20.0), and Bi(III) (log K(1) = 26.2). The low values of log K(1) for PDA with Al(III) and Ga(III) are because these ions are too small for the cleft in PDA, which requires a large metal ion with an ionic radius (r(+)) of 1.0 A. In(III) and Fe(III) (r(+) = 0.86 and 0.72 A for a coordination number (CN) of 7) are somewhat too small for the cleft in PDA but may adapt by increasing the coordination number, which increases the metal ion size, and have high log K(1) values. Very large log K(1) values are found, as expected, for Bi(III) (r(+) = 1.17 A, CN = 8), which fits the cleft quite well. Fluorescence studies show that Y(III) produces the largest CHEF (chelation enhanced fluorescence) effects, followed by La(III) and Lu(III), in the PDA complexes. Metal ions with nonfilled d or f subshells produce very large quenching of the fluorescence, as do heavy-metal ions such as In(III) and Bi(III), which have large spin-orbit coupling effects. The Al(III)/PDA complex produced an intense broad band at longer wavelength than the pi*-pi emissions of the PDA ligand, which is at a maximum at pH 6, and the possibility that this might reflect an exciplex, where one PDA ligand in the Al(III) complex pi-stacks with the excited state of a second PDA ligand, is discussed.

Imidazole-Annelated Ferrocene Derivatives as Highly Selective and Sensitive Multichannel Chemical Probes for Pb(II) Cations

New ferrocenyl-containing imidazopyridine and imidazophenazine receptors 2-5 show high selective affinity for Pb(II) ions over a range of other metal ions examined through different channels. Imidazopyridine-ferrocene dyad 2 behaves as a highly selective redox, chromogenic, and fluorescent chemosensor molecule for Pb(2+) cations: the oxidation redox peak is anodically shifted (DeltaE(1/2) = 150 mV), and the low energy band of the absorption spectrum is red-shifted (Deltalambda = 44 nm) upon complexation with this metal cation. This change in the absorption spectrum is accompanied by a color change from colorless to orange, which allows the potential for "naked eye" detection. The emission spectrum undergoes an important chelation-enhanced fluorescence (CHEF) effect (CHEF = 620), with an unprecedented detection limit of 2.7 microg L(-1). The presence of Zn(2+) cations also induced a perturbation of the redox potential, absorption, and emission spectra although in less extension than those found with Pb(2+) cations. Imidazophenazine-ferrocene dyad 3 has also shown its ability for sensing Pb(2+) cations through redox (DeltaE(1/2) = 120 mV), absorption (Deltalambda = 23 nm), and emission (CHEF = 133) channels, whereas the presence of Zn(2+) only has a little effect on the emission spectrum (CHEF = 74). The electrochemical changes observed in the two-armed ferrocenes 4 and 5 upon complexation show that the potential shift is higher for Zn(2+) ions (DeltaE(1/2) = 190-170 mV) than for Pb(2+) ions (DeltaE(1/2) = 180-110 mV), which is in clear contrast to those observed for the monoarmed ferrocenes 2 and 3. The recognition properties of the two-armed imidazopyridine-ferrocene triad 4 are quite similar to those exhibited by the parent monosubstituted receptor 2, and the most salient features are a strong perturbation of the redox wave (DeltaE(1/2) = 180 mV), a dramatic increasing of the fluorescent quantum yield (Phi(complex)/Phi(ligand) = 890) in the presence of Pb(2+), while the optical responses toward Zn(2+) cations were silent. The two-armed imidazophenazine-ferrocene triad 5 senses Pb(2+) cations through perturbation of the oxidation potential of the Fe(II)/Fe(III) redox couple (DeltaE(1/2) = 110 mV), important blue shift (Deltalambda = 160 nm) of the high energy band in the absorption spectrum, and a remarkable increase of the emission band (CHEF = 220), whereas smaller changes were observed in the presence of Zn(2+) cations. (1)H NMR studies as well as DFT calculations have been carried out to get information about which molecular sites are involved in the binding event.

A new selective fluorescent probe for lead ions

A new fluorescent probe (BPb 1) for Pb 2+ has been synthesized, where diethanolamine (receptor) is linked with 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene (BODIPY) (fluorophore) via a methylene group (spacer). The absorption (496 nm) and emission (505 nm) wavelengths are in visible range. The fluorescence quantum yields of the lead-free and lead-bound states of BPb 1 in acetonitrile are 0.013 and 0.693, respectively. The large chelation enhanced fluorescence effect (CHEF) with Pb 2+ can be explained by the blocking of the photoinduced electron transfer (PET) process.

Possible Steric Control of the Relative Strength of Chelation Enhanced Fluorescence for Zinc(II) Compared to Cadmium(II): Metal Ion Complexing Properties of Tris(2-quinolylmethyl)amine, a Crystallographic, UV−Visible, and Fluorometric Study

The idea is examined that steric crowding in ligands can lead to diminution of the chelation enhanced fluorescence (CHEF) effect in complexes of the small Zn(II) ion as compared to the larger Cd(II) ion. Steric crowding is less severe for the larger ion and for the smaller Zn(II) ion leads to Zn-N bond length distortion, which allows some quenching of fluorescence by the photoinduced electron transfer (PET) mechanism. Some metal ion complexing properties of the ligand tris(2-quinolylmethyl)amine (TQA) are presented in support of the idea that more sterically efficient ligands, which lead to less M-N bond length distortion with the small Zn(II) ion, will lead to a greater CHEF effect with Zn(II) than Cd(II). The structures of [Zn(TQA)H(2)O](ClO(4))(2).1.5 H(2)O (1), ([Pb(TQA)(NO(3))(2)].C(2)H(5)OH) (2), ([Ag(TQA)(ClO(4))]) (3), and (TQA).C(2)H(5)OH (4) are reported. In 1, the Zn(II) is 5-coordinate, with four N-donors from the ligand and a water molecule making up the coordination sphere. The Zn-N bonds are all of normal length, showing that the level of steric crowding in 1 is not sufficient to cause significant Zn-N bond length distortion. This leads to the observation that, as expected, the CHEF effect in the Zn(II)/TQA complex is much stronger than that in the Cd(II)/TQA complex, in contrast to similar but more sterically crowded ligands, where the CHEF effect is stronger in the Cd(II) complex. The CHEF effect for TQA with the metal ions examined varies as Zn(II) >> Cd(II) >> Ni(II) > Pb(II) > Hg(II) > Cu(II). The structure of 2 shows an 8-coordinate Pb(II), with evidence of a stereochemically active lone pair, and normal Pb-N bond lengths. In 3, the Ag(I) is 5-coordinate, with four N-donors from the TQA and an oxygen from the perchlorate. The Ag(I) shows no distortion toward linear 2-coordinate geometry, and the Ag-N bonds fall slightly into the upper range for Ag-N bonds in 5-coordinate complexes. The structure of 4 shows the TQA ligand to be involved in pi-stacking between quinolyl groups from adjacent TQA molecules. Formation constants determined by UV-visible spectroscopy are reported in 0.1 M NaClO(4) at 25 degrees C for TQA with Zn(II), Cd(II), and Pb(II). When compared with other similar ligands, one sees that, as the level of steric crowding increases, the stability decreases most with the small Zn(II) ion and least with the large Pb(II) ion. This is in accordance with the idea that TQA has a moderate level of steric crowding and that steric crowding increases for TQA analogs tris(2-pyridylmethyl)amine (TPyA) < TQA < tris(6-methyl-2-pyridyl)amine (TMPyA).

A highly selective fluorescent chemosensor for silver(I) in water/ethanol mixture

Synthesis, photophysical, and complexation properties of fluorescent chemosensors, L 1 and L 2 , with ‘receptor-spacer-fluorophore’ motif ( L 1 : NS 2O 2-cyclic receptor, L 2 : acyclic analogue receptor) are described. Maximum chelation-enhanced fluorescence effect (TURN-ON type) was observed in the presence of Ag + for both fluoroionophores in a 1:1 (v/v) aqueous ethanol solution: remarkably superior selectivity of L 1 (150-fold) with cyclic receptor than that of the L 2 (50-fold) with acyclic analogue was found. According to the fluorescence and NMR titrations, the excellent selectivity of L 1 is attributed to its topology-based higher affinity in complexation.

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.

Enhanced Metal Ion Selectivity of 2,9-Di-(pyrid-2-yl)-1,10-phenanthroline and Its Use as a Fluorescent Sensor for Cadmium(II)

The metal ion complexing properties of the ligand DPP (2,9-di-(pyrid-2-yl)-1,10-phenanthroline) were studied by crystallography, fluorimetry, and UV-visible spectroscopy. Because DPP forms five-membered chelate rings, it will favor complexation with metal ions of an ionic radius close to 1.0 A. Metal ion complexation and accompanying selectivity of DPP is enhanced by the rigidity of the aromatic backbone of the ligand. Cd2+, with an ionic radius of 0.96 A, exhibits a strong CHEF (chelation enhanced fluorescence) effect with 10(-8) M DPP, and Cd2+ concentrations down to 10(-9) M can be detected. Other metal ions that cause a significant CHEF effect with DPP are Ca2+ (10(-3) M) and Na+ (1.0 M), whereas metal ions such as Zn2+, Pb2+, and Hg2+ cause no CHEF effect with DPP. The lack of a CHEF effect for Zn2+ relates to the inability of this small ion to contact all four donor atoms of DPP. The structures of [Cd(DPP)2](ClO4)2 (1), [Pb(DPP)(ClO4)2H2O] (2), and [Hg(DPP)(ClO4)2] (3) are reported. The Cd(II) in 1 is 8-coordinate with the Cd-N bonds to the outer pyridyl groups stretched by steric clashes between the o-hydrogens on these outer pyridyl groups and the central aromatic ring of the second DPP ligand. The 8-coordinate Pb(II) in 2 has two short Pb-N bonds to the two central nitrogens of DPP, with longer bonds to the outer N-donors. The coordination sphere around the Pb(II) is completed by a coordinated water molecule, and two coordinated ClO4(-) ions, with long Pb-O bonds to ClO4(-) oxygens, typical of a sterically active lone pair on Pb(II). The Hg(II) in 3 shows an 8-coordinate structure with the Hg(II) forming short Hg-N bonds to the outer pyridyl groups of DPP, whereas the other Hg-N and Hg-O bonds are rather long. The structures are discussed in terms of the fit of large metal ions to DPP with minimal steric strain. The UV-visible studies of the equilibria involving DPP and metal ions gave formation constants that show that DPP has a higher affinity for metal ions with an ionic radius close to 1.0 A, particularly Cd(II), Gd(III), and Bi(III), and low affinity for small metal ions such as Ni(II) and Zn(II). The complexes of several metal ions, such as Cd(II), Gd(III), and Pb(II), showed an equilibrium involving deprotonation of the complex at remarkably low pH values, which was attributed to deprotonation of coordinated water molecules according to: [M(DPP)(H2O)]n+ <==> [M(DPP)(OH)](n-1)+ + H+. The tendency to deprotonation of these DPP complexes at low pH is discussed in terms of the large hydrophobic surface of the coordinated DPP ligand destabilizing the hydration of coordinated water molecules and the build-up of charge on the metal ion in its DPP complex because of the inability of the coordinated DPP ligand to hydrogen bond with the solvent.

New acridine derivatives bearing immobilized azacrown or azathiacrown ligand as fluorescent chemosensors for Hg 2+ and Cd 2+

Two new acridine derivatives bearing azacrown or azathiacrown ligand were synthesized as fluorescent chemosensors for Hg 2+ and Cd 2+ in aqueous solution. Compounds 1 and 2 displayed selective CHEF (chelation enhanced fluorescence) effects with Hg 2+ or Cd 2+ among the metal ions examined. The practical use of these probes was demonstrated by their applications to the detection of Hg 2+ and Cd 2+ ions in mammalian cells.

A Highly Fluorescent Anthracene‐Containing Hybrid Material Exhibiting Tunable Blue–Green Emission Based on the Formation of an Unusual “T‐Shaped” Excimer

A series of flexible bis(9-anthryldiamine) ligands (L1-L3) linked with alkyl spacers of different chain length was synthesized and characterized, in order to investigate the coordination behavior of these diamine ligands with metal ions (Zn2+, etc.) based on fluorescence measurements. The results showed that, in the case of anthryldiamine ligands bearing two- or four-carbon links, the zinc ion induced a chelation-enhanced fluorescence (CHEF) effect in aqueous media, while a trace amount of water could selectively quench the blue emission of the Zn(II) complex with a three-carbon-linked ligand (1). Meanwhile, the introduction of more water (concentration >11 %) resulted in the formation of a new green luminescent species; the luminescence intensity was enhanced stepwise to a maximum with addition of approximately 30 % water in THF solution. The peak position (centered at approximately 500 nm) and the lifetime measurement (tau=19.59 ns) indicated that the green luminescence was attributable to a novel edge-to-face dimeric conformation ("T-shaped" conformation) of anthracene, and not to the more common face-to-face dimeric conformation. Accordingly, 1H NMR spectroscopic studies in nonaqueous or aqueous solution confirmed this T-shaped conformation, which is consistent with the results of single-crystal X-ray structure analysis and solid-state photoluminescence studies.

Synthesis of porphyrin-appended terpyridine as a chemosensor for cadmium based on fluorescent enhancement

The design and synthesis of a porphyrin-appended terpyridine, 5-(4-([2,2′:6′,2″]-terpyridin-4-yl-carboxyamidyl)phenyl)-10,15,20-triphenylporphyrin (H 2TPPTPy) and its application as potential fluoroionophore for recognition of metal ions are reported. For preparation of the fluoroionophore, a novel simple strategy with improved total yield has been applied for the synthesis of 2,2′:6′,2″-terpyridine-4′-carboxylic acid as a ligand. H 2TPPTPy shows chelation-enhanced fluorescence effect with cadmium ion via the interruption of photoinduced electron transfer (PET) process, which has been utilized as the basis of the fabrication of the Cd(II)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Cd(II)-sensitive chemosensor were investigated. It shows a linear response toward Cd(II) in the concentration range of 3.2 × 10 −6 to 3.2 × 10 −4 M with a limit of detection of 1.2 × 10 −6 M. The chemosensor shows good selectivity for Cd(II) over a large number of cations, such as alkali, alkali earth and transitional metal ions except Cu(II) and Zn(II). The sensor has been used for determination of Cd(II) in water samples with satisfactory recoveries.

A new acridine derivative as a fluorescent chemosensor for zinc ions in an 100% aqueous solution: a comparison of binding property with anthracene derivative

A new acridine derivative was synthesized as a fluorescent chemosensor for Zn 2+ in an 100% aqueous solution. Compound 1 displayed a selective CHEF (chelation enhanced fluorescence) effect with Zn 2+, on the other hand, a similar anthracene derivative 2 did not display any significant change with the metal ions examined.

Ratiometric Zn2+ Sensor and Strategy for Hg2+ Selective Recognition by Central Metal Ion Replacement

Strategies of both self-assembly and metal ion replacement were adopted in the development of new metal ion sensors for Zn2+ and Hg2+. Ligand BPBA, phenylene-bridged bis(pyrrol-2-ylmethyleneamine), could self-assemble to form a molecular square in the presence of Zn2+, which showed strong emission in solution. The fluorescent emission of formed BPBA-Zn2+ dropped with the addition of Hg2+. BPBA could be a good Zn2+ sensor candidate and BPBA-Zn2+ could be a good Hg2+ sensor candidate based on the mechanisms of the chelation-enhanced fluorescence effect and the replacement of central metal ion induced chelation-enhanced fluorescence quenching effect, respectively.

New BODIPY Derivatives as OFF−ON Fluorescent Chemosensor and Fluorescent Chemodosimeter for Cu2+: Cooperative Selectivity Enhancement toward Cu2+

New 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) derivatives (1 and 2) were synthesized as an "off-on" fluorescent chemosensor and fluorescent chemodosimeter for Cu2+ and Pb2+. Compound 1 displayed selective and large chelation enhanced fluorescence effects with Pb2+ and Cu2+ among the metal ions examined. On the other hand, compound 2, a fluorescent chemodosimeter, effectively recognized Cu2+ via a selective hydrolysis of the acetyl group.

Molecular taekwondo. 2. A new calix[4]azacrown bearing two different binding sites as a new fluorescent ionophore.

Synthesis and binding studies of a new calixarene-based fluoroionophore were made. Calix[4]azacrown having an anthracenyl unit displayed large chelation-enhanced fluorescence effects with Cs(+), Rb(+), and K(+) over other metal ion tested. Interesting "molecular taekwondo" processes between Cs(+)-Cu(2+) and Cs(+)-Ag(+) pairs were monitored via fluorescent changes.