Synthesis and Luminescence of Novel Eu<sup>III</sup> Complexing Agents and Labels with 4‐(Phenylethynyl)pyridine Subunits

Takalo, Harri; Hemmilä, Ilkka; Sutela, Timo; Latva, Martti

doi:10.1002/hlca.19960790321

Cited by 60 publications

(35 citation statements)

References 33 publications

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“…[3] The introduction of the phenylethynyl group into a fluorescent molecule usually leads to a bathochromic shift in absorbance and emission, as well as an increase in the quantum yield of emission. This has been shown for naphthalene, [15] anthracene and tetracene, [16] pyrene, [17] perylene, [18] 2-phenylbenzoxazole, [19] bimanes, [20] Eu III chelates, [21] coumarins, [22] BODIPY, [23] and fluorescein. [24] Suitably functionalized phenylethynyl derivatives of pyrene and anthracene could be promising tools for the development of fluorescent probes for structural studies of nucleic acids.…”

Section: Introductionmentioning

confidence: 66%

1‐(Phenylethynyl)pyrene and 9,10‐Bis(phenylethynyl)anthracene, Useful Fluorescent Dyes for DNA Labeling: Excimer Formation and Energy Transfer

et al. 2004

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A series of novel modifying reagents, including phosphoramidites and solid supports, have been synthesized, and used for the introduction of 1‐(phenylethynyl)pyrene (PEPy) and 9,10‐bis(phenylethynyl)anthracene (BPEA) fluorescent dyes into predetermined positions of synthetic oligonucleotides. These two fluorophores have been shown to constitute an energy donor−acceptor pair, and can be used as such in fluorescent oligonucleotide probes, designed for the detection and structural studies of nucleic acids. The sensitivity of the probe to duplex formation is demonstrated. The formation of the PEPy and BPEA excimers is reported for the first time on nucleic acids. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Introductionmentioning

confidence: 66%

1‐(Phenylethynyl)pyrene and 9,10‐Bis(phenylethynyl)anthracene, Useful Fluorescent Dyes for DNA Labeling: Excimer Formation and Energy Transfer

et al. 2004

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“…Although sensitized emission has been studied in detail for Eu 3ϩ and Tb 3ϩ complexes, [6,7,34] and efficient antennachromophores with appropriate triplet energy levels have been reported, the field of sensitized near-infrared lanthanide luminescence is still relatively unexplored. The main difference between the sensitization of Eu 3ϩ and Tb 3ϩ and the sensitization of Nd 3ϩ , Yb 3ϩ , and Er 3ϩ is that the former require chromophores with triplet states above about 22,000 cm -1 , whereas the latter lanthanide ions can be excited through chromophores with much lower triplet states (see Figure 1).…”

Section: ؉ Complexesmentioning

confidence: 99%

Near-Infrared and Visible Luminescence from Terphenyl-Based Lanthanide(III) Complexes Bearing Amido and Sulfonamido Pendant Arms

et al. 2000

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A series of m‐terphenyl‐based ligands bearing three coordinating oxyacetate and two amido or two sulfonamido groups, (1a‐b)H3 and (2)H3, respectively, have been synthesized and characterized. The structures of the corresponding neutral complexes have been studied using 1H‐NMR spectroscopy and luminescence experiments. The photophysical properties of the (1a‐b)Eu, (2)Eu, (1a)Tb, and (2)Tb complexes have been studied to determine the structure of the first coordination sphere in methanol. The first coordination sphere consists of eight donor atoms provided by the ligand (three chelating oxyacetate groups and two amide or sulfonamide oxygens), and one methanol molecule. The (1a)Dy and (1a)Sm complexes exhibited sensitized luminescence in the visible spectral region, but the luminescence intensity was very sensitive to quenching by C‐H groups. The near‐infrared emitting (1a)Ln and (2)Ln complexes exhibited sensitized luminescence at wavelengths (at 880, 1060, and 1330 nm for Nd3+, at 980 nm for Yb3+, and at 1550 nm for Er3+) of interest for applications in optical telecommunication devices. The luminescence lifetimes of these complexes in DMSO and [D6]DMSO are in the range of microseconds. The luminescent state of the NIR emitting lanthanide ions is very efficiently quenched by high frequency oscillators (such as C‐H groups) in the solvent and the ligand.

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“…This ligand is potentially octadentate for the coordination of Ln III ions and contains pyridine units that can be easily functionalized with groups able to conjugate with biological material. [16,17] The corresponding lanthanide complexes were characterized by 1 H and 13 C NMR techniques in D 2 O solution. Luminescence studies have been carried out to test the ability of the ligand to promote a good antenna effect for Eu III and Tb III , as well as to determine the hydration number of the complexes in solution.…”

Section: Introductionmentioning

confidence: 99%

Lanthanide Chelates Containing Pyridine Units with Potential Application as Contrast Agents in Magnetic Resonance Imaging

Platas‐Iglesias

Mato‐Iglesias

Djanashvili

et al. 2004

Chemistry A European J

107

128

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A new pyridine-containing ligand, N,N'-bis(6-carboxy-2-pyridylmethyl)ethylenediamine-N,N'-diacetic acid (H(4)L), has been designed for the complexation of lanthanide ions. (1)H and (13)C NMR studies in D(2)O solutions show octadentate binding of the ligand to the Ln(III) ions through the nitrogen atoms of two amine groups, the oxygen atoms of four carboxylates, and the two nitrogen atoms of the pyridine rings. Luminescence measurements demonstrate that both Eu(III) and Tb(III) complexes are nine-coordinate, whereby a water molecule completes the Ln(III) coordination sphere. Ligand L can sensitize both the Eu(III) and Tb(III) luminescence; however, the quantum yields of the Eu(III)- and Tb(III)-centered luminescence remain modest. This is explained in terms of energy differences between the singlet and triplet states on the one hand, and between the 0-phonon transition of the triplet state and the excited metal ion states on the other. The anionic [Ln(L)(H2O)]- complexes (Ln=La, Pr, and Gd) were also characterized by theoretical calculations both in vacuo and in aqueous solution (PCM model) at the HF level by means of the 3-21G* basis set for the ligand atoms and a 46+4 f(n) effective core potential for the lanthanides. The structures obtained from these theoretical calculations are in very good agreement with the experimental solution structures, as demonstrated by paramagnetic NMR measurements (lanthanide-induced shifts and relaxation-rate enhancements). Data sets obtained from variable-temperature (17)O NMR at 7.05 T and variable-temperature (1)H nuclear magnetic relaxation dispersion (NMRD) on the Gd(III) complex were fitted simultaneously to give insight into the parameters that govern the water (1)H relaxivity. The water exchange rate (k(298)(ex)=5.0 x 10(6) s(-1)) is slightly faster than in [Gd(dota)(H2O)]- (DOTA=1,4,7,10-tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclododecane). Fast rotation limits the relaxivity under the usual MRI conditions.

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Synthesis and Luminescence of Novel Eu^III Complexing Agents and Labels with 4‐(Phenylethynyl)pyridine Subunits

Cited by 60 publications

References 33 publications

1‐(Phenylethynyl)pyrene and 9,10‐Bis(phenylethynyl)anthracene, Useful Fluorescent Dyes for DNA Labeling: Excimer Formation and Energy Transfer

1‐(Phenylethynyl)pyrene and 9,10‐Bis(phenylethynyl)anthracene, Useful Fluorescent Dyes for DNA Labeling: Excimer Formation and Energy Transfer

Near-Infrared and Visible Luminescence from Terphenyl-Based Lanthanide(III) Complexes Bearing Amido and Sulfonamido Pendant Arms

Lanthanide Chelates Containing Pyridine Units with Potential Application as Contrast Agents in Magnetic Resonance Imaging

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Synthesis and Luminescence of Novel EuIII Complexing Agents and Labels with 4‐(Phenylethynyl)pyridine Subunits

Cited by 60 publications

References 33 publications

1‐(Phenylethynyl)pyrene and 9,10‐Bis(phenylethynyl)anthracene, Useful Fluorescent Dyes for DNA Labeling: Excimer Formation and Energy Transfer

1‐(Phenylethynyl)pyrene and 9,10‐Bis(phenylethynyl)anthracene, Useful Fluorescent Dyes for DNA Labeling: Excimer Formation and Energy Transfer

Near-Infrared and Visible Luminescence from Terphenyl-Based Lanthanide(III) Complexes Bearing Amido and Sulfonamido Pendant Arms

Lanthanide Chelates Containing Pyridine Units with Potential Application as Contrast Agents in Magnetic Resonance Imaging

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Synthesis and Luminescence of Novel Eu^III Complexing Agents and Labels with 4‐(Phenylethynyl)pyridine Subunits