One dimensional energy transfer in lanthanoid picolinates. Correlation of structure and spectroscopy

Sendor, Dorota; Hilder, Matthias; Juestel, Thomas; Junk, Peter Courtney; Kynast, Ulrich

doi:10.1039/b302499g

Cited by 62 publications

(44 citation statements)

References 30 publications

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“…Indeed for all known and related compounds, when these chelating moieties are not present, 2- [14] and 3D [15][16][17][18][19][20][21][22] materials are typically isolated. The picolinic acid residues appear coordinated to the Sm 3+ metallic centres in a typical N,O-chelating fashion (Scheme 1) with a bite angle of 64.97(10)°, a value consistent with those reported for similar compounds [23][24][25][26] (10 entries in the CSD, with values spanning from 60.5 to 67.6°; median of 64.0°).…”

Section: Crystal Structure Description Of [Sm(glu)(pic)(h 2 O) 2 ]supporting

confidence: 76%

“…10 %, with a corresponding k r value of 0.253 ms -1 . These values, lifetimes and quantum efficiency values, although lower when compared with those obtained by Sendor et al for the europium picolinato, [8] are of the same order of magnitude as those obtained for the Eu 3+ emission in the 3-hydroxypicolinato [7] and 2-hydroxynicotinato complexes.…”

Section: +supporting

confidence: 66%

“…Each spectrum displays a large broad band in the range of 250-Sm 3+ , Eu 3+ and Tb 3+ energy levels. The large broad bands can be ascribed to the excited levels of the ligands [24,26] and are mainly formed of two components, peaking around 275 and 295 nm, being most evident for the Eu 3+ and Tb…”

Section: Photoluminescencementioning

confidence: 99%

“…[7] Picolinic acid complexes of lanthanides, particularly those of Eu 3+ and Tb 3+ , show interesting photoluminescent behaviour because energy transfer from the aromatic groups close to the lanthanide ions may enhance the luminescent efficiency of the ion. [8] Even dispersed in solid matrices they can produce efficient luminescent materials, such as those in SiO 2 nanoparticles obtained by the sol-gel method. [7] Therefore, in principle, it should be possible to fine tune the luminescence of such nanocomposites by working out the coordination chemistry of the Ln complexes.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterisation and Luminescent Properties of Lanthanide‐Organic Polymers with Picolinic and Glutaric Acids

et al. 2007

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Three new lanthanide(III) complexes (Ln = Sm, Tb and Eu) of picolinic and glutaric acid were prepared and characterised. The crystal structure of the complex [Sm(glu)(pic)(H2O)2] (where Hpic and H2glu stand for picolinic and glutaric acid, respectively) was determined by single‐crystal X‐ray diffraction. All the Ln complexes were characterised by elemental analysis, infrared spectroscopy, X‐ray powder diffraction and thermoanalytical measurements. The combined data show that these Ln complexes are isostructural. The effect of both organic ligands on the photoluminescent behaviour of the Sm3+, Eu3+ and Tb3+ complexes is discussed and we anticipate the possibility of controlling the photoluminescence of picolinic‐containing lanthanide compounds by systematically varying the length of the bridging ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Crystal Structure Description Of [Sm(glu)(pic)(h 2 O) 2 ]supporting

confidence: 76%

Section: +supporting

confidence: 66%

Section: Photoluminescencementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterisation and Luminescent Properties of Lanthanide‐Organic Polymers with Picolinic and Glutaric Acids

et al. 2007

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“…For example, we have shown that in the coordination polymer Na[Tb(pic) 4 ]·1.5H 2 O (picH = 2-picolinic acid) one-dimensional energy migration occurs, which can be utilised to transfer energy to Eu 3+ if the latter is co-doped into the material. [19] However, co-doping is only successful in these compounds, if the structural integrity of the parent compound is not compromised, a factor, which we have observed in the above-mentioned picolinates, if lanthanum was introduced. Therefore, we typically address the structural characteristics of several of the lanthanoid series.…”

Section: Co-coordinated Complexesmentioning

confidence: 83%

Synthesis, Structural and Spectroscopic Studies on the Lanthanoid p‐Aminobenzoates and Derived Optically Functional Polyurethane Composites

et al. 2007

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Aromatic carboxylates of the rare earths are known for highly efficient luminescence, thus holding the promise of applicability in optical devices, but may be problematic to apply as such due to their structure, which is polymeric in nature. Therefore, means of conversion into molecular species or eventually polymer embeddings are sought, while at the same time maintaining their advantageous optical features. For these purposes, co‐ligations of rare earth p‐aminobenzoates with bidentate bipyridine and phenanthroline, tridentate terpyridine and polyurethanes, which may also be perceived as polydentate ligands, have been carried out. The materials were characterised with focus on their structure and optical performance. Brightly luminescing composites were obtained from reactions with aromatic and aliphatic diisocyanates. Prolonged UV‐irradiation of the materials proved hexamethylene diisocyanates to be superior with regard to photodegradation. Transparent polyurethane monoliths with emission quantum yields between 40 % and 55 % were eventually prepared from covalent attachement of Tb(p‐aminobenzoate)3 and its bipyridine co‐ligated complexes to a hexamethylene diisocyanate/polyol system. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Förster‐Type Energy Transfer along a Specified Axis

Minkowski

Calzaferri

2005

Angewandte Chemie

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Förster transfer of electronic excitation energy in 3D [1][2][3] and 2D [4,5] systems has been studied in many laboratories. Kuhn extended the Förster theory of long-range energy transfer in 3D systems to 2D and 1D systems.[6] The theory of the time dependence of this process in 1D and 2D cases was studied by Hauser et al. [7] and later extended to fractal dimensions by several groups. [8,9] Nevertheless, only little experimental evidence has been published to prove 1D energy transfer. In the strict sense, one-dimensionality can be understood as a transport along a line or at least along an isolated file. However, one-dimensionality in the 3D space of an object of, for example, cylindrical morphology can also mean that the nett transport of the individual transfer steps goes along the c axis of the cylinder, that is, along a well-defined axis. We call this quasi-1D to avoid any confusion.One way to try to realize the conditions in which quasi-1D transport of excitation energy should be favored is by using dye molecules in a crystalline host that consists of 1D channels. Panchromatic chromophore mixtures in an AlPO 4 -5 molecular sieve show interesting luminescence properties. [10] We have shown that zeolite L, with its 1D channels, is a very versatile material with which to build artificial host-guest antenna systems.[11] The channels are occupied by energy-transporting dyes (donors, D) and energy-trapping dyes (acceptors, A); strongly luminescent dyes are usually selected. The energy-transfer process that occurs when an excited donor transports its excitation energy to an unexcited acceptor proceeds with a Förster-type mechanism and its rate constant k DA can be expressed according to Equation (1), in which f D and t D are thefluorescence quantum yield and lifetime, respectively, of the donor, J DA is the spectral overlap integral between the donor emission and the acceptor absorption spectra, k DA describes the relative orientation of the electronic transition moments, and R DA is the distance between D and A. R DA has a strong effect on the energy-transfer rate constant. It can be tuned, for example, by varying the loading of the dye molecules [12] , which changes the overall dye-dye distance. Another elegant way to study the distance dependence of the transfer of excitation energy is to introduce a spacer molecule between the donors and the acceptors to separate them locally, as illustrated in Figure 1. To realize this introduction, a defined quantity of acceptor molecules was first incorporated into the channels of zeolite L. In the second step, different quantities of spacer molecules were incorporated into the channels that already contained acceptor dyes, thus forming spacer layers of different thicknesses. In the third step, the same quantity of donor dyes was always added. As the conditions are such that the dyes cannot glide past each other, the crystal is divided into compartments in which the density of one dye is dominant. By selectively exciting the donor, the behavior of the excitation energy can ...

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One dimensional energy transfer in lanthanoid picolinates. Correlation of structure and spectroscopy

Cited by 62 publications

References 30 publications

Synthesis, Characterisation and Luminescent Properties of Lanthanide‐Organic Polymers with Picolinic and Glutaric Acids

Synthesis, Characterisation and Luminescent Properties of Lanthanide‐Organic Polymers with Picolinic and Glutaric Acids

Synthesis, Structural and Spectroscopic Studies on the Lanthanoid p‐Aminobenzoates and Derived Optically Functional Polyurethane Composites

Förster‐Type Energy Transfer along a Specified Axis

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