Synthesis, sparkle model, intensity parameters and spectroscopic studies of the new Eu(fod) 3 phen-NO complex

Mesquita, Maria Eliane de; Júnior, Severino Alves; Júnior, N.B.C.; Freire, Ricardo O.; Silva, F.R.G. e; Sá, Gilberto F. de

doi:10.1016/s0022-4596(02)00206-2

Cited by 25 publications

(10 citation statements)

References 25 publications

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“…The structure was solved by direct (7) 40 (2) N (3) 3752 (12) 8852 (10) 2582 (8) 45 (2) O(1) -1024(10) 10439 (7) 1486 (6) 39 (2) O(2) 1972(10) 8061 (7) 349 (6) 40 (2) O (3) 1308 (8) 10465 (6) 41 (6) 31 (2) O(4) -1016 (11) 7846 (8) 1589 (7) 49 (2) O (5) 3898 (9) 8336 (8) 1966 (8) 46 (2) O (6) 2357 (11) 9240 (10) 2783 (8) 56 (2) O (7) 4888 (13) 8991 (11) 2943 (9) 66 (3) C(1) -1755 (13) 11526 (10) 717 (9) 33 (2) C (2) -2401 (17) 12464 (12) 1089 (10) 49 (3) C (3) -2713 (14) 11964 (10) 2312 (9) 36 (2) C(4) -1700 (20) 11800 (17) 3179 (14) 71 (5) C ( methods. All non-hydrogen atoms were refined anisotropically by the...…”

Section: Methodsmentioning

confidence: 99%

“…In addition, we can also achieve a molecular assembly of ternary or quaternary lanthanide complex systems with ligands as molecular fragments [17][18][19][20]. Recently, a hydrothermal method has become a fascinating reaction technology to be used in the synthesis of coordination compounds, which can realize some novel structural lanthanide complexes comparing to the general solution evaporation [21,22].…”

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A Strong Luminescent Quaternary Dimeric Complex [Tb(BAA)2(Phen)(NO3)]2: Hydrothermal Synthesis, Structure, and Photophysics

2005

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1 As an active area of research for decades, lanthanides differ from other fluorogens in optical properties, such as long luminescence lifetimes and narrow emission bands in the visible or near-infrared [1][2][3] region, which are appropriate for applications as fluorescent probes [4,5] in biology and medicine and active centers for luminescent materials. Along with the rising considerable attention in the design and assembly of lanthanide complexes, a lot of multichromophoric ligand systems involved in light absorption to lead to highly luminescent complexes of rare-earth ions have been developed [6][7][8][9][10][11][12]. For instance, in the case of Bipy or Phen (Bipy is 2,2'-bipyridine, Phen is 1,10-phenanthroline) components as assistant ligands, the chromophores (L) are arranged to fulfill the coordination requirements of lanthanide (Ln) cations; thus, an antenna-to-cation sensitization step (i.e., an L-to-Ln energy transfer) occurs between partners in a somehow rigid coordination environment. However, a strong quenching of their luminescence is unavoidable in aqueous environments.Many different types of crystal structure of ternary lanthanide complexes with aromatic acids and nitrogen-containing ligands, which show an intense fluorescent character and whose crystals are stable in air, were obtained. Aromatic carboxylic acids provide chelated carboxylates having the capability of more coordinated oxygen atoms, such that higher coordination numbers can be obtained by decreasing molar ratio of ligands, resulting in the dimer or coordination polymer [13][14][15][16].1 This article was submitted by the authors in English.In addition, we can also achieve a molecular assembly of ternary or quaternary lanthanide complex systems with ligands as molecular fragments [17][18][19][20]. Recently, a hydrothermal method has become a fascinating reaction technology to be used in the synthesis of coordination compounds, which can realize some novel structural lanthanide complexes comparing to the general solution evaporation [21,22].In this paper, we report the hydrothermal synthesis of a novel luminescent quaternary dimeric complex [ Tb ( BAA ) 2 ( Phen )( NO 3 )] 2 ( I ) with the assembly of benzoyl acetic acid (BAA), 1,10-phenanthroline and terbium nitrate. The detailed crystal structure and photophysical properties are presented in detail. EXPERIMENTALAll reagents were of analytical grade and used without further purification, except for stock hydrated terbium nitrates prepared by the reaction of lanthanide oxides Tb 4 O 7 and nitric acid.Compound I was prepared by mixing hydrated terbium nitrates, benzoyl acetic acid, and 1,10-phenanthroline in a molar ratio 2 : 3 : 2 in deionized water, and its pH was controlled in a range of 3-4 with a 0.2 mol/l NaOH solution. Stirring of the mixture for 2 h gave a white precipitate, which in succession was placed in a 25 ml Teflon-lined reactor and heated at 433 K in an oven for 3 days. Yellow columnar crystals that formed were studied by X-ray diffraction analysis at room temperatur...

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

A Strong Luminescent Quaternary Dimeric Complex [Tb(BAA)2(Phen)(NO3)]2: Hydrothermal Synthesis, Structure, and Photophysics

2005

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“…These empty volumes lead to the isolation of the molecule and fit the vacuum conditions, which is a condition in quantum chemistry calculations . This europium compound has a very intense hypersensitive 5 D 0 -7 F 2 transition in relation to the 5 D 0 -7 F 1 magnetic allowed transition and has been recently studied in our group [5,6]. Combining the acetate media and this very efficient red emitter, one has a probe for both spectroscopic investigation and quantum chemistry calculations.…”

Section: Introductionmentioning

confidence: 99%

“…Combining the acetate media and this very efficient red emitter, one has a probe for both spectroscopic investigation and quantum chemistry calculations. The Sparkle model [6][7][8][9] has then been applied in order to calculate the ground state geometry of the complex. By using the simulated coordinates of the central ion and its nearest neighbors we have calculated the crystal field and intensity parameters (B k q , O l ) and the 5 D 0 -7 F 1 transition splitting (DE 021 ) and the spontaneous emission coefficient (Einstein coefficient) (A rad ) in the frame of the simple overlap model (SOM) [10][11][12][13][14][15].…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic properties of the Eu(fod)3Phen–NO incorporated carboxylate glass

Beltrão

Santos

Mesquita

et al. 2006

Journal of Luminescence

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“…25,26 Besides, Sparkle/AM1 calculations are hundreds of times faster, 15 and have been recently employed for the study of quantum yields of luminescence. [27][28][29][30][31][32][33][34] However, although AM1 generally produces satisfactory results and its trustworthiness has been extensively timetested, other semiempirical models may prove more advantageous for some particular applications.PM3 35,36 is also a very popular semiempirical molecular orbital model, which predominantly gives enthalpies of formation with lower average errors than AM1. Indeed, PM3 has a wide following and is available in a variety of quantum chemical softwares, both commercial and non-commercial.…”

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confidence: 99%

Sparkle/PM3 for the modeling of europium(III), gadolinium(III), and terbium(III) complexes

Freire¹,

Rocha

Simas³

2009

J. Braz. Chem. Soc.

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O modelo Sparkle/PM3 é parametrizado para complexos de európio (III), gadolínio (III) e térbio (III). A validação do modelo foi realizada utilizando noventa e seis complexos de Eu(III), setenta complexos de Gd(III) e quarenta e dois complexos de Tb(III); todos a partir de estruturas cristalográficas de alta qualidade, com fator R < 5%. Os erros médios absolutos, obtidos com o modelo Sparkle/PM3, considerando todas as distâncias interatômicas do tipo lantanídeo-átomo ligante, foram 0,080 Å para Eu(III), 0,063 Å para Gd(III) e 0,070 Å para Tb(III). Estes valores médios são similares aos obtidos com o modelo Sparkle/AM1 (0,082 Å, 0,061 Å, e 0,068 Å, respectivamente). Além disso, a exatidão em reproduzir o poliedro de coordenação de complexos de Eu(III), Gd(III) e Tb(III) é similar à obtida utilizando métodos ab initio com potenciais efetivos de caroço. Finalmente, com o objetivo de avaliar se as geometrias preditas com o modelo Sparkle/PM3 são confiáveis, escolhemos um dos complexos de Eu(III), BAFZEO, para o qual geramos centenas de diferentes geometrias iniciais, onde variamos de forma aleatória as distâncias e ângulos entre os ligantes e o íon Eu(III). Em seguida, todas essas geometrias iniciais foram otimizadas usando o modelo Sparkle/PM3. Como resultado, observamos uma tendência significativa onde a geometria que apresentou o menor erro médio absoluto apresentou também a energia total mais baixa, o que reforça a validade do modelo Sparkle.The Sparkle/PM3 model is extended to europium(III), gadolinium(III), and terbium(III) complexes. The validation procedure was carried out using only high quality crystallographic structures, for a total of ninety-six Eu(III) complexes, seventy Gd(III) complexes, and forty-two Tb(III) complexes. The Sparkle/PM3 unsigned mean error, for all interatomic distances between the trivalent lanthanide ion and the ligand atoms of the first sphere of coordination, is: 0.080 Å for Eu(III); 0.063 Å for Gd(III); and 0.070 Å for Tb(III). These figures are similar to the Sparkle/AM1 ones of 0.082 Å, 0.061 Å, and 0.068 Å respectively, indicating they are all comparable parameterizations. Moreover, their accuracy is similar to what can be obtained by present-day ab initio effective core potential full geometry optimization calculations on such lanthanide complexes. Finally, we report a preliminary attempt to show that Sparkle/PM3 geometry predictions are reliable. For one of the Eu(III) complexes, BAFZEO, we created hundreds of different input geometries by randomly varying the distances and angles of the ligands to the central Eu(III) ion, which were all subsequently fully optimized. A significant trend was unveiled, indicating that more accurate local minima geometries cluster at lower total energies, thus reinforcing the validity of sparkle model calculations. Keywords:Sparkle model, AM1, PM3, lanthanide complexes, rare earth coordination compounds IntroductionLanthanide complexes of the trivalent ions of europium, gadolinium, and terbium display a wide range of applications, with newer one...

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Synthesis, sparkle model, intensity parameters and spectroscopic studies of the new Eu(fod) 3 phen-NO complex

Cited by 25 publications

References 25 publications

A Strong Luminescent Quaternary Dimeric Complex [Tb(BAA)2(Phen)(NO3)]2: Hydrothermal Synthesis, Structure, and Photophysics

A Strong Luminescent Quaternary Dimeric Complex [Tb(BAA)2(Phen)(NO3)]2: Hydrothermal Synthesis, Structure, and Photophysics

Spectroscopic properties of the Eu(fod)3Phen–NO incorporated carboxylate glass

Sparkle/PM3 for the modeling of europium(III), gadolinium(III), and terbium(III) complexes

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