Energy Transfer Luminescence of Europium(<scp>III</scp>) and Terbium(<scp>III</scp>) Cryptates of Macrobicyclic Polypyridine Ligands

Alpha, Béatrice; Lehn, Jean‐Maríe; Mathis, Gérard

doi:10.1002/anie.198702661

Cited by 328 publications

(116 citation statements)

References 26 publications

Supporting

Mentioning

110

Contrasting

Unclassified

Order By: Relevance

“…For instance, cryptand-type ligands containing 2,2Ј-bipyridine combine the shielding effect upon complexation and the sensitizer 'antenna' moiety of the bipyridine groups. [8][9][10] Crystal structures of these Eu 3+ and Tb 3+ cryptates are consistent with the 'antenna effect: ' 11 the cation is encapsulated inside the cavity of ligand, and makes short contacts (from 2·55 to 2·90 Å) with the eight N pyridine atoms. Its coordination sphere is completed by two Cl Ϫ anions, or by one Cl Ϫ and one H 2 O molecule.…”

Section: Introductionsupporting

confidence: 60%

Molecular Dynamics Study of the Complexation of Luminescent Cations by Encapsulating Ligands With Bipyridine Units

Fraternali¹,

Wipff²

1997

J. Phys. Org. Chem.

View full text Add to dashboard Cite

Based on MD simulations, the structures of Eu 3+ and EuCl 3 complexes of bipyridine-substituted calixarenes in different environments (in vacuo and in acetonitrile and water solutions) were modelled. The data account for the differences in their luminescence properties. The role of the calixarene platform, preorganization of the ligands, and an explicit account of counterions in different environments are analysed.

show abstract

Section: Introductionsupporting

confidence: 60%

Molecular Dynamics Study of the Complexation of Luminescent Cations by Encapsulating Ligands With Bipyridine Units

Fraternali¹,

Wipff²

1997

J. Phys. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…In the solid state, these latter moieties formed a neutral bimetallic entity which was characterised for Tb by an X-ray structure determination and luminescence spectroscopy. The bipyridine moieties are confirmed as providing a good antenna effect 21 and the formation of an extended network of H-bonded bimetallic entities in the 2 : 3 compounds opens the way for tailoring compartmental ligands bearing H 2 L units or bipyridine monocarboxylic acids and programmed for the formation of extended interactions at a nanometric scale.…”

Section: Resultsmentioning

confidence: 87%

Structural and photophysical properties of LnIII complexes with 2,2′-bipyridine-6,6′-dicarboxylic acid: surprising formation of a H-bonded network of bimetallic entities†

Bünzli

Charbonnière

Ziessel

2000

J. Chem. Soc., Dalton Trans.

View full text Add to dashboard Cite

The ligand H 2 L = 2,2Ј-bipyridine-6,6Ј-dicarboxylic acid reacts with Ln(NO 3 ) 3 ؒxH 2 O (x = 6, Ln = Eu, Tb; x = 5, Ln = Gd) in MeOH/Et 3 N to give complexes with 1 : 2 and 2 : 3 metal : ligand stoichiometry, (which have been isolated and characterised. A sizeable quantum yield is obtained for the 1 : 2 Eu : Ligand complex in aqueous solution (Q Eu abs = 11.5 ± 2.3% at pH = 6.6), pointing to an efficient ligand-to-metal energy transfer. The presence of some inner-sphere interaction with water was deduced from Eu( , sensitisation of Tb III also occurs (Q Tb abs = 6.3 ± 1.3% at pH = 6.6) but the Tb( 5 D 4 ) excited level is de-populated at room temperature by a back-transfer process to the ligand. The crystal structure obtained for the 2 : 3 Tb : ligand complex evidences two distinct terbium sites, one Tb III being complexed to two ligands affording a mono-anionic complex, itself linked to the second terbium ion with a µ-carboxylate bridge; the generic formulation of the crystallised complex is [TbL 2 -µ-TbL(H 2 O) 3 ]ؒ2H 2 Oؒ 2MeOH. Consecutive dimers are linked by an elaborate network of H-bonds involving interstitial solvent molecules. A photophysical study of the 2 : 3 Eu : Ligand complex in the solid state points to the same structural features, revealing two metal ion sites with essentially no bonded water (q = 0.3, site I) and with 3 co-ordinated water molecules (q = 2.8, site II), respectively. The H 2 L synthon is therefore an interesting building block for the design of elaborate compartmental ligands and/or of supramolecular functional assemblies.

show abstract

“…1 70 (s, 3H, CH 3 ), 4.18 (s, 3H, OCH 3 ), 4.62 (s, 4H, CH 2 OH), 7.16 (s, 2H, ArH) ppm. 13 The organic layers were combined and dried over MgSO 4 . After removal of the solvents and recrystallization (MeOH), the product was obtained as an off-white powder.…”

Section: Generalmentioning

confidence: 99%

Predicting Efficient Antenna Ligands for Tb(III) Emission

Samuel

Raymond

2008

Inorg. Chem.

View full text Add to dashboard Cite

ABSTRACT:A series of highly luminescent Tb(III) complexes of para-substituted 2-hydroxyisophthalamide ligands (5LI-IAM-X) has been prepared (X = H, CH 3 , (C=O)NHCH 3 , SO 3 -, NO 2 , OCH 3 , F, Cl, Br) to probe the effect of substituting the isophthalamide ring on ligand and Tb(III) emission in order to establish a method for predicting the effects of chromophore modification on Tb(III) luminescence. The energies of the ligand singlet and triplet excited states are found to increase linearly with the -withdrawing ability of the substituent. The experimental results are supported by 2 time-dependent density functional theory (TD-DFT) calculations performed on model systems, which predict ligand singlet and triplet energies within ~5% of the experimental values. The quantum yield () values of the Tb(III) complex increases with the triplet energy of the ligand, which is in part due to the decreased non-radiative deactivation caused by thermal repopulation of the triplet. Together, the experimental and theoretical results serve as a predictive tool that can be used to guide the synthesis of ligands used to sensitize lanthanide luminescence.

show abstract

Energy Transfer Luminescence of Europium(III) and Terbium(III) Cryptates of Macrobicyclic Polypyridine Ligands

Cited by 328 publications

References 26 publications

Molecular Dynamics Study of the Complexation of Luminescent Cations by Encapsulating Ligands With Bipyridine Units

Molecular Dynamics Study of the Complexation of Luminescent Cations by Encapsulating Ligands With Bipyridine Units

Structural and photophysical properties of LnIII complexes with 2,2′-bipyridine-6,6′-dicarboxylic acid: surprising formation of a H-bonded network of bimetallic entities†

Predicting Efficient Antenna Ligands for Tb(III) Emission

Contact Info

Product

Resources

About