Lanthanide Complexes in Molecular Recognition and Chirality Sensing of Biological Substrates

Tsukube, Hiroshi; Shinoda, Satoshi

doi:10.1021/cr010450p

Cited by 612 publications

(297 citation statements)

References 155 publications

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“…4 The design of organic photosensitisers has dominated the development of smart lanthanide-based optical devices in view of their high molar absorption coefficients, flexibility of molecular design, as well as their efficient sensitization ability of the metalcentred luminescence. In particular, this approach allows the enhancement of the emission intensity and quantum yield of nearinfrared (NIR) emitting lanthanide ions.…”

Section: Introductionmentioning

confidence: 99%

Sensitized near-IR luminescence of lanthanide complexes based on push-pull diketone derivatives

et al. 2010

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Lanthanide complexes with two push-pull diketone derivatives as sensitizers have been developed as synthons for near-infrared emitting materials. The ligand substituents consist of a carbazole moiety with hole-transport properties and an aromatic or heteroaromatic unit. According to quantitative NMR analysis and complementary HPLC experiments, the diketones are predominantly in their enolic form in polar solvents such as THF and MeCN at room temperature. The preferred cis-enol form contributes strongly to the binding of lanthanide ions (Ln = Nd, Gd, Er). The resulting tris(diketonate) ternary complexes with terpyridine (Ln = Nd, Er) display sizeable near-IR emission with long luminescence lifetimes.

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Section: Introductionmentioning

confidence: 99%

Sensitized near-IR luminescence of lanthanide complexes based on push-pull diketone derivatives

et al. 2010

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“…These characteristics enable them to have wide application in responsive luminescent stains for biomedical analysis with temporal and spectral discrimination, [1][2][3][4][5][6][7][8][9] and to find use in development for liquid-crystal displays, [10][11][12][13] laser materials [14][15] and optoelectronic emitters. [16][17] Generally, the excellent luminescence properties of lanthanide complexes are attributed to the intramolecular energy transfer between the organic ligands and chelated metal ("antenna effect").…”

Section: Introductionmentioning

confidence: 99%

Listening to Lanthanide Complexes: Determination of the Intrinsic Luminescence Quantum Yield by Nonradiative Relaxation

Yang

Liu

et al. 2008

ChemPhysChem

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The photophysical properties of lanthanide complexes have been studied extensively; however, fundamental parameters such as the intrinsic quantum yield as well as radiative and nonradiative decay rates are difficult or even impossible to measure experimentally. Herein, a photoacoustic (PA) method is proposed to determine the intrinsic quantum yield of lanthanide complexes with lifetimes in the order of milliseconds. This method is used to determine the intrinsic quantum yields for europium(III)‐containing metallomesogens as well as terbium(III) complexes. The results show that the PA signal is sensitive to both the lifetime and the ratio of the fast‐to‐slow heat component of the samples. It is found that there is an efficient ligand sensitization and a moderate intrinsic quantum yield for the complexes. The intrinsic quantum yield of Eu3+ in the metallomesogens exhibits an obvious increase upon the isotropic liquid to smectic A transition. The proposed PA method is quite simple, and can contribute to a clearer understanding of the photophysical processes in luminescent lanthanide complexes.

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“…There has been growing interest in the design and synthesis of lanthanide-based coordination polymers motivated by their fascinating structure and the exploitable applications in luminescent materials, molecular adsorption, bimetallic catalysis and so on [1][2][3][4][5][6].T he polycarboxylic ligands have been proved to be extremelyversatile organicligands due to thefactthattheycan exhibit flexible coordination modes, including chelating, bidentate bridging or chelating bridging modes [7,8]. As an extension of research toward rational design and preparation of lanthanide coordination polymer, we recently have isolated anovel three-dimensional terbium (III) coordinated polymer containing two types of ligands (pyridine-2,5-dicarboxylate and picolinate) [Tb(C 7 H 3 NO 4 )(C 6 H 4 NO 2 )(H 2 O)] n under ionothermal conditions using the ionicliquid1-ethyl-3-methylimidazolium([Emim]Br) as solvent.Asillustrated in theFigure,the asymmetricunit of title compound contains one Tb(III) cation, one pyridine-2,5-dicarboxylate anion, one picolinate anion and one coordinated water molecule.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of poly[aqua-(μ4-pyridine-2,5-dicarboxylato- κ5N,O:O’:O’’:O’’’)-(μ2-picolinato-κ2O:O’)-terbium(III)], C13H9N2O7Tb

Song

2015

Zeitschrift Für Kristallographie - New Crystal Structures

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C 13 H 9 N 2 O 7 Tb, monoclinic, P2 1 /c (no. 14), a =9.2251 (7) Source of materialAll chemicals were of reagent grade quality obtained from commercial sources and were used without further purification. The title compound was prepared under ionothermal conditions using the ionic liquid 1-ethyl-3-methylimidazolium ([Emim]Br) as solvent. The title compound was prepared from am ixture of terbium(III) nitrate hexahydrate (0.45 g, 1m mol), pyridine-2,5-dicarboxylic acid (0.24 g, 1.5 mmol), nicotinic acid (0.25 g, 2 mmol) and [Emim]Br (1.0 g, 5.23 mmol). The mixture was stirred for half an hour, and then transferred into aTeflon-lined stainless steel autoclave (50 ml)and heated at 438 Kfor 7d.After the mixture had been cooled slowly to room temperature, colourless rodshaped crystals were obtained. The product was filtered off, washed with deionized water and dried in avacuum desiccator at ambient temperature (yield 36 %, based on terbium(III) nitrate hexahydrate). It is worth noting that, the title compound can also be obtained using ionic liquid 1-methyl-3-butylimidazolium bromide ([Bmim]Br) as solvent. In order to confirm the chemical composition of the title compound, C, H, and Nelements analysis were performedo naP erkinElmer 2400II elemental analyzer. Anal.c alcd.( %) for C 13 H 9 N 2 O 7 Tb: C, 33.64; H, 1.95; N, 6.04. Found (%): C, 33.91; H, 1.69; N, 5.88. The results support the formula of the title compound. Experimental detailsThe Hatomsbonded to Cwere positioned geometrically and refined using ariding model, with C-H =0.93 Åand with U iso (H) = 1.2 times U eq (C). The Hatoms bonded to O1W were located from Fourierd ifferencem apsa nd refinedw ithd istancer estraintso f O1W-H1WA=0.83 Åand O1W-H1WB=0.83 Å. DiscussionThere has been growing interest in the design and synthesis of lanthanide-based coordination polymers motivated by their fascinating structure and the exploitable applications in luminescent materials, molecular adsorption, bimetallic catalysis and so on [1-6].T he polycarboxylic ligands have been proved to be extremelyversatile organicligands due to thefactthattheycan exhibit flexible coordination modes, including chelating, bidentate bridging or chelating bridging modes [7,8]. As an extension of research toward rational design and preparation of lanthanide coordination polymer, we recently have isolated anovel three-dimensional terbium (III) coordinated polymer containing two types of ligands (pyridine-2,5-dicarboxylate and picolinate) [Tb(C 7 H 3 NO 4 )(C 6 H 4 NO 2 )(H 2 O)] n under ionothermal conditions using the ionicliquid1-ethyl-3-methylimidazolium([Emim]Br) as solvent.Asillustrated in theFigure,the asymmetricunit of title compound contains one Tb(III) cation, one pyridine-2,5-dicarboxylate anion, one picolinate anion and one coordinated water molecule. Within the structure, Tb(III) cation is coordinated by seven oxygen atomsand one Natom,exhibiting adistorted bicapped trigonal prismatic geometry, among which, six oxygen atomsare derived from carboxylate groups and one oxygen at...

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Lanthanide Complexes in Molecular Recognition and Chirality Sensing of Biological Substrates

Cited by 612 publications

References 155 publications

Sensitized near-IR luminescence of lanthanide complexes based on push-pull diketone derivatives

Sensitized near-IR luminescence of lanthanide complexes based on push-pull diketone derivatives

Listening to Lanthanide Complexes: Determination of the Intrinsic Luminescence Quantum Yield by Nonradiative Relaxation

Crystal structure of poly[aqua-(μ4-pyridine-2,5-dicarboxylato- κ5N,O:O’:O’’:O’’’)-(μ2-picolinato-κ2O:O’)-terbium(III)], C13H9N2O7Tb

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