Dimethyl sulphoxide complexes of lanthanide and yttrium nitrates

Ramalingam, S.; Soundararajan, S.

doi:10.1016/0022-1902(67)80220-3

Cited by 69 publications

(29 citation statements)

References 20 publications

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“…It is interesting to note that all the three nitrate groups are bidentates in contradiction to the earlier suggestion (Ramalingam & Soundararajan, 1967) that only one nitrate ion is likely to be bidentate. The coordination polyhedron formed by the ten oxygen atoms is shown in Fig.…”

Section: Description Of the Structure (A) Coordination Around La 3+contrasting

confidence: 48%

“…The dimethyl sulphoxide is found to coordinate through the oxygen atom as suggested from infrared studies (Ramalingam & Soundararajan, 1967). These groups are found to be pyramidal.…”

Section: (B ) Dimethyl Sulphoxide Moleculementioning

confidence: 74%

“…This, we hoped, would also add to our understanding of the coordination geometry and crystal chemistry of lanthanons. As part of the programme, a series of complexes of dimethyl sulphoxide with lanthanide nitrates, prepared and characterized earlier in this laboratory (Ramalingam & Soundararajan, 1967), has been taken up for X-ray structural studies. These complexes have the general formula Ln(NO3)3. n(DMSO), where n=4 for Ln=La to Gd, n=3 for Ln=Y, Ho and Yb and DMSO is (CH3)2SO.…”

Section: Introductionmentioning

confidence: 99%

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Crystal and molecular structure of a dimethyl sulphoxide complex with lanthanum nitrate, La(NO₃)₃.4(CH₃)₂SO

Bhandary¹,

Manohar²

1973

Acta Crystallogr Sect B

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The crystal structure of the complex La(NO3)3.4(CH3)2SO has been solved by the heavy-atom method. The complex crystallizes in the monoclinic space group C2/e with four formula units in a unit cell of dimensions a= 14.94, b= 11.04, c= 15.54 A and fl= 109 ° 10'. The parameters have been refined by threedimensional least-squares procedures with anisotropic thermal parameters for all atoms except hydrogen. The final R index for 1257 observed reflexions is 0.094. The La 3 + ion is coordinated by ten oxygen atoms with La-O distances varying from 2.47 to 2.71 A. The geometry of the coordination polyhedron is described.

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Section: Description Of the Structure (A) Coordination Around La 3+contrasting

confidence: 48%

“…The dimethyl sulphoxide is found to coordinate through the oxygen atom as suggested from infrared studies (Ramalingam & Soundararajan, 1967). These groups are found to be pyramidal.…”

Section: (B ) Dimethyl Sulphoxide Moleculementioning

confidence: 74%

Section: Introductionmentioning

confidence: 99%

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Crystal and molecular structure of a dimethyl sulphoxide complex with lanthanum nitrate, La(NO₃)₃.4(CH₃)₂SO

Bhandary¹,

Manohar²

1973

Acta Crystallogr Sect B

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“…Tetrahydrofuran was distilled over Na and acetonitrile was treated with CaH 2 and P 2 O 5 . 38 The dmso adducts of the lanthanoid salts were prepared from the oxides (Rhône-Poulenc, 99.99%) 39 and their lanthanoid content determined by titration with Titriplex III (Merck) in the presence of urotropine (1,3,5,7-tetraazatricyclo[3.3.1.1 3,7 ]decane) and xylene orange.…”

Section: Experimental Synthesis and Characterisation Of The Complexesmentioning

confidence: 99%

Complexes of p-tert-butylcalix[5]arene with lanthanides: synthesis, structure and photophysical properties †

Charbonnière¹,

Balsiger²,

Schenk³

et al. 1998

J. Chem. Soc., Dalton Trans.

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Spectrophotometric pK a determination for p-tert-butylcalix [5]arene (H 5 L) in acetonitrile (pK a1 = 11.5 ± 0.7, pK a2 = 15.4 ± 1.0 at 298 K) evidenced both intra-and inter-molecular stabilisation of the deprotonated forms. Dimeric complexes [Ln 2 (H 2 L) 2 (dmso) 4 ] (Ln = Eu III , GdIII , or Tb III; dmso = dimethyl sulfoxide) were isolated from tetrahydrofuran (thf) in the presence of NaH as base. A single-crystal analysis of [Eu 2 (H 2 L) 2 (dmso) 4 ]ؒ 10thf showed the deformation of the cone conformation of the calixarene upon complexation and co-ordination of dmso molecules by inclusion through the hydrophobic cavity of the ligand. A photophysical investigation revealed a total quenching of the metal luminescence by a ligand-to-metal charge-transfer state in the case of Eu III while luminescence of Tb III is sensitised (quantum yield in thf: 5.1%). The temperature-dependent lifetime of Tb III is analysed in terms of a potential metal-to-ligand back-transfer process.The cyclic framework of calixarenes, 1 associated with the presence of phenol oxygen donor atoms, affords an interesting platform for the complexation of metal atoms, 2 while the hydrophobic cavity allows the inclusion of charged 3 and neutral 4 organic guests. The relative facility with which calixarenes can be partially or totally functionalised at the upper or lower rims, coupled with their easy large-scale synthesis, at least for the even members of the series (n = 4, 6 or 8), has opened further perspectives for their use in supramolecular chemistry. 5In particular, the hard acid character of the lower rim makes calixarenes interesting potential ligands for the complexation of trivalent lanthanide ions, either for extraction purposes 6 or for the design of efficient lanthanide-based luminescent devices.7-9 Antenna effects 10 can be generated directly by the phenol units or by lower or upper rim substitution.Previous work on the complexation of lanthanides with calix[n]arenes has mainly focused on the four-, six-and eightmembered systems. While p-tert-butylcalix [8] 19 who isolated water-soluble inclusion complexes between p-sulfonatocalix [5]arene with La, Gd, Eu, Tb and Yb and showed by X-ray crystallography that the interaction is either outer sphere or occurs exclusively via one sulfonato functionality, the metal centre acting often as a bridging brick. In this paper we present the isolation and the structural and photophysical properties of lanthanoid() (Ln = Eu, Gd or Tb) phenolate-bonded inner-sphere complexes with p-tert-butylcalix [5]arene (H 5 L). The reported data add valuable information on the interaction between lanthanoid() ions and p-tert-butylcalix [n]arenes and demonstrate that multiple bonds between the ligand and the metal ions can be generated only in the presence of a strong base. In addition, the spectrophotometric determination of the first two pK a values of the ligand is reported. Results and Discussion Acid-base behaviour of H 5 L in acetonitrileThe compound H 5 L was titrated at 298 K by Et 3 N in acetonitril...

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“…[28] It is soluble in several organic solvents, such as acetonitrile, and partially decomposes in water, by replacement of some SCN À ligands by water molecules.…”

Section: Yttrium(iii) Trifluoromethanesulfonate Enneahydrate ([Y(h 2 mentioning

confidence: 99%

Geometrical Structure of Yttrium and Metal-Bromine Complexes in Solution: Limitations of Extended X-ray Absorption Fine Structure Analysis (EXAFS)

Chaboy¹,

Muñoz‐Páez²,

Díaz‐Moreno³

2001

Chem. Eur. J.

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An extensive study on the appearance of multi-electron features in the X-ray absorption spectra of several yttrium(III)-based compounds has been performed. The existence of a multi-electron transition of non-negligible intensity within the extended X-ray absorption fine structure (EXAFS) region of the Y K-edge spectra has been proven. The impact of such features in the EXAFS analysis is made evident for aqueous solutions of YBr3 x 6H2O in liquid and glassy states in the concentration range 0.005-2.0 M, in which this transition induces an overestimation in the coordination numbers derived from EXAFS. We have performed theoretical computation of cross-sections for the double-electron processes at the K-edge of both Y and Br. These computations have been applied to the experimental EXAFS K-edge spectra of both Y and Br in several solids and in aqueous solutions. While in the case of Y K-edge spectra the presence of such multi-electron transitions was seen to seriously affect the standard EXAFS analysis, its influence in the case of Br K-edge spectra was determined to be negligible.

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Dimethyl sulphoxide complexes of lanthanide and yttrium nitrates

Cited by 69 publications

References 20 publications

Crystal and molecular structure of a dimethyl sulphoxide complex with lanthanum nitrate, La(NO₃)₃.4(CH₃)₂SO

Crystal and molecular structure of a dimethyl sulphoxide complex with lanthanum nitrate, La(NO₃)₃.4(CH₃)₂SO

Complexes of p-tert-butylcalix[5]arene with lanthanides: synthesis, structure and photophysical properties †

Geometrical Structure of Yttrium and Metal-Bromine Complexes in Solution: Limitations of Extended X-ray Absorption Fine Structure Analysis (EXAFS)

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Dimethyl sulphoxide complexes of lanthanide and yttrium nitrates

Cited by 69 publications

References 20 publications

Crystal and molecular structure of a dimethyl sulphoxide complex with lanthanum nitrate, La(NO3)3.4(CH3)2SO

Crystal and molecular structure of a dimethyl sulphoxide complex with lanthanum nitrate, La(NO3)3.4(CH3)2SO

Complexes of p-tert-butylcalix[5]arene with lanthanides: synthesis, structure and photophysical properties †

Geometrical Structure of Yttrium and Metal-Bromine Complexes in Solution: Limitations of Extended X-ray Absorption Fine Structure Analysis (EXAFS)

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Crystal and molecular structure of a dimethyl sulphoxide complex with lanthanum nitrate, La(NO₃)₃.4(CH₃)₂SO

Crystal and molecular structure of a dimethyl sulphoxide complex with lanthanum nitrate, La(NO₃)₃.4(CH₃)₂SO