New Luminescent Lanthanide Tetrakis-Complexes NEt4 [LnL4 ] Based on Dimethyl-N-Benzoylamidophosphate.

New lanthanide dimethyl-N-benzoylamidophosphate (HL) based tetrakis-complexes NEt4 [LnL4 ] (Ln3+ =La, Nd, Sm, Eu, Gd, Tb, Dy) are reported. The complexes are characterized by means of NMR, IR, absorption, and luminescent spectroscopy as well as by elemental, X-Ray, and thermal gravimetric analyses. The phenyl groups of the four ligands of the complex anion are directed towards one side, while the methoxy groups are directed in the opposite side, which makes the complexes under consideration structurally similar to calixarenes. The effect of changing the alkali metal counterion to the organic cation NEt4+ on the structure and properties of the tetrakis-complex [LnL4]- is analyzed. The complexes exhibit bright characteristic for respective lanthanides luminescence. Rather high intensity of the band of 5 D0 →7 F4 transition, observed in the luminescence spectrum of NEt4 [EuL4 ], is discussed based on theoretical calculations.

Structures and Spectral and Magnetic Properties of a Series of Carbacylamidophosphate Pentanuclear Lanthanide(III) Hydroxo Complexes.

A series of pentanuclear lanthanide complexes Ln5L6(µ-L)4(µ3-OH)4(µ4-OH) (LnIII = Nd, Dy, Ho, Er, Yb; L- = dimethyl N-benzoylamidophosphate ion, [C6H5C(O)-N-P(O)(OCH3)2]-) was obtained by the reaction of sodium dimethyl N-benzoylamidophosphate with the corresponding lanthanide nitrates. The pentanuclear cores formed as a result of self-arrangement and their composition did not depend on the lanthanide ion. The complexes and sodium dimethyl N-benzoylamidophosphate have been characterized by single-crystal X-ray diffraction. The absorption spectra of the complexes were measured at 300 and 4 K. The dysprosium and ytterbium complexes exhibited weak emission in the visible and IR regions, respectively. Temperature dependences of magnetic susceptibility (χM) of the dysprosium, holmium, and erbium compounds were studied. It was found that χM vs T dependences were governed by the crystal field splitting effects with the Δ parameter being in the range 5-17 cm-1. Slow magnetic relaxation was found for the dysprosium complex by ac magnetic measurements, while no significant out-of-phase signals were detected for holmium and erbium complexes.

Crystal structure of N-(di-phenyl-phosphor-yl)-2-meth-oxy-benzamide.

In the title compound, C20H18NO3P, the C=O and P=O groups of the carbacyl-amido-phosphate (CAPh) fragments are located in a synclinal position relative to each other and are pre-organized for bidentate chelate coordination of metal ions. The N-H group is involved in the formation of an intra-molecular hydrogen bond. In the crystal, mol-ecules do not form strong inter-molecular inter-actions but the mol-ecules are linked via weak C-H⋯π inter-actions, forming chains along [001].

Tris(N-{bis-[meth-yl(phen-yl)amino]-phosphor-yl}benzene-sulfonamidato-κ2O,O')(1,10-phenanthroline-κ2N,N')lanthanum(III).

The asymmetric unit of [La(C20H21N3O3PS)3(C12H8N2)] is created by one LaIII ion, three deprotonated N-{bis-[meth-yl(phen-yl)amino]-phosphor-yl}benzene-sulfonamidate (L-) ligands and one 1,10-phenanthroline (Phen) mol-ecule. Each LaIII ion is eight-coordinated (6O+2N) by three phosphoryl O atoms, three sulfonyl O atoms of three L- ligands and two N atoms of the chelating Phen ligand, leading to the formation of six- and five-membered metallacycles, respectively. The lanthanum coordination polyhedron has a bicapped trigonal-prismatic geometry. 'Sandwich-like' intra-molecular π-π stacking inter-actions are observed between the 1,10-phenanthroline ligand and two benzene rings of two different L- ligands. The phenyl rings of L- that are not involved in the stacking inter-actions show minor positional disorder. Mol-ecules form layers parallel to the (010) plane due to weak C-H⋯O inter-molecular hydrogen bonds. Unidentified highly disordered solvate mol-ecules that occupy ca 400 Å3 large voids have been omitted from the refinement model.

Contribution of Energy Transfer from the Singlet State to the Sensitization of Eu3+ and Tb3+ Luminescence by Sulfonylamidophosphates.

A series of stable lanthanide complexes Na[Ln(L)4 ] (Ln=La3+ , Eu3+ , Gd3+ , Tb3+ , with L=dimethyl(4-methylphenylsulfonyl)amidophosphate and dimethyl-2-naphthylsulfonylamidophosphate) were synthesized. The compounds were characterized by single-crystal X-ray diffraction, IR, absorption, and emission spectroscopy at 293 and 77 K. In contrast to the usual and well-known dominant role of the ligand triplet state in intramolecular energy transfer processes in Ln complexes, in this particular new class of Ln compounds with sulphonylamidophosphate ligands, strong experimental and detailed theoretical evidence suggest a dominant role is played by the ligand first excited singlet state. The importance of the role played by the 7 F5 level in the case of the Tb3+ compound in this process is shown. The theoretical approach for the energy transfer rates was successfully applied to the rationalization of the experimental data. The higher-lying excited levels of Eu (5 DJ , 5 LJ , 5 GJ ) and Tb (5 DJ , 5 GJ , 5 LJ , 5 HJ , 5 FJ , 5 IJ ) were included in the calculations for the first time. Both the multipolar and exchange mechanisms were taken into account. The experimental intensity parameters (Ωλ ), emission lifetimes (τ), radiative (Arad ) and non-radiative (Anrad ) decay rates, and quantum yields (theoretical and experimental) were determined and are discussed in detail.

Tris[dimethyl (benzoyl-amido)-phosphato-κ(2) O,O'](1,10-phenanthroline-κ(2) N,N')neodymium(III).

In both independent mol-ecules of the title compound, [Nd(C9H11NO4P)3(C12H8N2)], the Nd(III) atom is coordinated by six O atoms belonging to three phosphoryl ligands and two N atoms of 1,10-phenanthroline in a dodeca-hedral geometry. In the phosphoryl ligands, the benzene rings are twisted with respect to the planes of the sp(2)-hybridized C atoms of the chelate rings by 12.1 (1)-24.7 (1)°.

Tetra-methyl N,N'-(2,2,3,3,4,4-hexa-fluoro-1,5-dioxopentane-1,5-di-yl)bis-(phospho-ramidate).

The mol-ecule of the title compound, C(9)H(14)F(6)N(2)O(8)P(2), lies on a twofold rotation axis that passes through the middle C atom of the three-atom fluoro-methyl-ene unit. The carbonyl and phosphoryl groups are in an antiperiplanar conformation. In the crystal, N-H⋯O=P hydrogen bonds link the mol-ecules into polymeric chains parallel to the c axis.

Tetra-methyl-ammonium dimethyl (phenyl-sulfonyl-amido)phosphate(1-).

The title compound, C(4)H(12)N(+)·C(8)H(11)NO(5)PS(-), was obtained from tetra-methyl-ammonium hydroxide and dimeth-yl(phenyl-sulfon-yl)amido-phosphate. The tetra-methyl-ammonium cation has a slightly distorted tetra-hedral configuration and the N-C bond lengths lie in the range 1.457 (3)-1.492 (3) Å. In the crystal, no classical hydrogen bonds are observed between the cation and the anion.

cis-Diaqua-bis-[dimethyl (phenyl-sulfonyl-imino)-phospho-nato]cobalt(II).

In the title diaqua-cobalt complex, [Co(C(8)H(11)NO(5)PS)(2)(H(2)O)(2)], the Co(II) atom is surrounded by six O atoms belonging to the phosphoryl and sulfonyl groups of two deprotonated chelate ligands and two additional O atoms from water mol-ecules which are in cis positions with respect to one another. The coordination environment of cobalt can be described as a distorted octa-hedron. O-H⋯O hydrogen bonds between the water and sulfonyl O atoms of neighboring mol-ecules form chains running parallel to [010]. Two methoxy groups attached to one phosphorus are disordered over two sets of sites in a 0.6:0.4 ratio.

catena-Poly[calcium-bis-[µ-N-(dimethyl-phosphino-yl)benzene-sulfonamidato]].

The crystal structure of the title calcium complex, [Ca(C(8)H(11)NO(5)PS)(2)](n), is composed of a polymeric chain, which is formed due to two bridging sulfonyl groups linking Ca(II) ions in a O-S-O-Ca manner. Thus, the coordination environment of the Ca(II) ions is composed of six O atoms belonging to the phosphoryl and sulfonyl groups of two chelate rings and two additional O atoms of two bridging sulfonyl groups. The coordination polyhedron of the central atom (2 symmetry) has a distorted octa-hedral geometry.