Victor A. Trush

X-Ray analysis and excited state dynamics in a new class of lanthanide mixed chelates of the type LnPhβ3·Phen (Ln=Sm, Eu, Gd, Tb)

A new type of lanthanide complex with a derivative of β-diketone and phenanthroline, LnPhβ3·Phen [where Phβ = CCl3–C(O)–N–P(O)–(OCH3)2; Phen = 1,10-phenanthroline, Ln = Sm, Eu, Gd, Tb] was synthesised. The X-ray diffraction analysis of the Sm(III) complex shows that it is in the monoclinic system and P21/c space group. There are two different Sm3+ ions with insignificant differences between the Sm–O, –N distances (0.005 A) and a CN = 8. Absorption, emission and emission excitation spectra at 293, 77 and 4.2 K were used to characterise the title compounds in the solid state and in solution. The luminescence spectra at 77 K for the Eu analogue are complex and two components in the 5D0 → 7F0 transition show that Eu3+ ions reside in two symmetry sites. The spectroscopic results correspond well to the crystal structure of the SmPhβ3·Phen compound and confirm that the Sm3+, Eu3+ and Tb3+ monocrystals are isostructural. Efficient energy transfer sensitises the interion emission from 5D4 or 5D0 levels of Tb(III) and Eu(III) after ligand band excitation. Based on the splitting of the levels observed at 4.2 K in the single crystal spectra of Tb and Eu, as well as the absorption, phosphorescence and excitation spectra, energy level diagrams are proposed. The mechanism of energy transfer and excited state dynamics are discussed. Strong vibronic coupling was observed mainly in the 7F0 → 5D2 electronic transition. The IR spectra were used to analyse the vibronic components. Analysis of the emission spectra of a Eu3+-doped silica sol-gel sample was made and compared to those for the title monocrystals. The total spectral characteristics of the materials permits an evaluation of their potential applicability.

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.

β-Diketonates and their Analogs: Stabilization of the Dimeric M2{L}4(D)2 (M = Co, Ni) Core in the Complexes with Dimethyl-N-trichloroacetylamidophosphate {Cl3C(O)NP(O)(OCH3)2}-

The coordination compounds of general formula [M{X}2(2-propanol)]2 (M = Co(II) (1), Ni(II) (2); {X} = Cl3CC(O)NP(O)(OCH3)2) have been prepared and characterized by means of IR, UV-VIS spectroscopy and X-ray analysis. The compounds are isomorphous according to X-ray powder diffraction studies. Crystal data for 1: triclinic, P1̄, with a = 9.510(2), b = 12.053(2), c = 23.594(5) Å ,a = 84.74(3), b = 86.47(3), g = 75.45(3)°, Z = 2, V = 2604.7(9) Å3, R1 = 0.067, wR2 = 0.143 for 6299 unique reflection used). The complex adopts a dimeric centrosymmetric molecular array with Co-O-Co bridges formed via the oxygen atoms of phosphoryl groups. This structure is stabilized by intradimeric hydrogen bonds of the type P = O---H with the coordinated 2-propanol. The metal atoms are coordinated in slightly distorted octahedra (Co-O 2.050(5)-2.140(5) Å). Unlike the β-diketonate compounds of similar structure, the dimeric complexes are stable towards donor species and in 2-propanol solution.

Structure of Tl(18-crown-6){Cl3CC(O)N P(O)(OCH3)2}: Coordination of the Ionic Multidentate Weakens the Interaction of the Metal Atom with the Crown Ether

The thallium(I) dimethyl-N-trichloroacetylamidophosphate complex with a 18-crown-6 of the composition Tl(18-crown-6){L} (L = {Cl3CC(O)NP(O)(OCH3)2} -) has been prepared and characterized by means of IR spectroscopy and X-ray diffraction (orthorhombic, space group P212121 with a = 8.660( 1), b = 11.557(2), c =26.296(3) Å, Z = 4, V = 2631.8(6) Å3; R1 = 0.0285 and wR2 = 0.0558 for 4314 unique reflections). It was shown that (L-) is coordinated to the central atom in a bidentate manner via oxygen atoms of phosphoryl [Tl-O(l) 2.678(4) Å] and carbonyl groups [Tl-O(2) 3.012(6) Å.The Tl( 18-crown-6)+ moiety adopts a typical “sunrise” coordination with the metal atom laying 1.134(2) Å above the mean plane of the oxygen atoms of the macrocycle. This deviation is the highest value of the structurally examined Tl( 18- crown-6 )+ complexes. The Tl-O (etheric) separations are in the range 2.913(4) - 3.198(5) Å (av. 3.030(6) Å).

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

In the title diaquacobalt complex, [Co(C8H11NO5PS)2(H2O)2], the CoII 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 molecules which are in cis positions with respect to one another. The coordination environment of cobalt can be described as a distorted octahedron. O—H⋯O hydrogen bonds between the water and sulfonyl O atoms of neighboring molecules 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.

Tris[dimethyl (benzoyl­amido)­phosphato-κ2O,O′](1,10-phenanthroline-κ2N,N′)neodymium(III)

In both independent molecules of the title compound, [Nd(C9H11NO4P)3(C12H8N2)], the NdIII atom is coordinated by six O atoms belonging to three phosphoryl ligands and two N atoms of 1,10-phenanthroline in a dodecahedral 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)°.

catena-Poly[calcium-bis­[μ-N-(dimethyl­phosphino­yl)benzene­sulfonamidato]]

The crystal structure of the title calcium complex, [Ca(C8H11NO5PS)2]n, is composed of a polymeric chain, which is formed due to two bridging sulfonyl groups linking CaII ions in a O—S—O—Ca manner. Thus, the coordination environment of the CaII 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 octahedral geometry.

Coordination compounds based on CAPh type ligand: synthesis, structural characteristics and luminescence properties of tetrakis-complexes CsLnL4 with dimethylbenzoylamidophosphate

Abstract Searching for prospective luminescent materials, the series of new lanthanide coordination compounds CsLnL4 (Ln = La, Pr, Nd, Sm – Er, and Yb; L− = {C6H5CONPO(OCH3)2}-) was synthesized. X-ray diffraction studies of CsNdL4 and CsYbL4 have been performed establishing polymeric structures of the tetrakis-complexes built from [LnL4]− anions and cesium cations functioning as linkers. The IR, absorption, emission, excitation spectra, and decay time measurements at 298 and 77 K, as well as thermal gravimetric analyses, were used to characterize the complexes.

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

The title compound, C4H12N+·C8H11NO5PS−, was obtained from tetramethylammonium hydroxide and dimethyl(phenylsulfonyl)amidophosphate. The tetramethylammonium cation has a slightly distorted tetrahedral 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.

Tris(N-{bis­[meth­yl(phen­yl)amino]­phosphor­yl}benzene­sulfonamidato-κ2O,O′)(1,10-phenanthroline-κ2N,N′)lanthanum(III)

A lanthanum(III) complex with formula LaL 3Phen (where L − is the sulfonylamidophosphate (SAPh)-type ligand N-{bis[methyl(phenyl)amino]phosphoryl}benzenesulfonamidate, C6H5SO2NHPO[N(CH3)C6H5]2 has been synthesized and its crystal structure determined.