ABSTRACT
A lutetium(III) complex based on the anion of the ligand dimethyl (2,2,2-tri-chloro-acet-yl)phospho-ramidate (HL) and tetra-phenylphosphonium, of composition PPh4[LuL 4] (L = CAPh = carbacyl-amido-phosphate), or (C24H20)[Lu(C4H6Cl3NO4P)4], has been synthesized and structurally characterized. The X-ray diffraction study of the compound revealed that the lutetium ion is surrounded by four bis-chelating CAPh ligands, forming the complex anion [LuL 4]- with a coordination number of 8[O] for LuIII, while PPh4 + serves as a counter-ion. The coordination geometry around the Lu3+ ion was determined to be a nearly perfect triangular dodeca-hedron. The complex crystallizes in the monoclinic crystal system, space group P21/c, with four mol-ecules in the unit cell. Weak hydrogen bonds Oâ¯HC(Ph), Clâ¯HC(Ph) and Nâ¯HC(Ph) are formed between the cations and anions. For a comparative study, HL-based structures were retrieved from the Cambridge Structural Database (CSD) and their geometries and conformations are discussed. A Hirshfeld surface analysis was also performed.
ABSTRACT
Materials based on Eu3+ and Tb3+ coordination compounds are of great interest due to their strong red and green luminescence. Appropriate selection of ligands plays a huge role in optimizing their photophysical properties. Another very helpful instrument for such optimization is theoretical modelling, which permits the prediction of the emissive properties of materials through intramolecular energy transfer analysis. The ligands that allow for achieving high efficiency of Eu3+ and Tb3+ emissions include carbacylamidophosphates (CAPh, HL). In this brief review, we summarize recent research for lanthanides CAPh-based coordination compounds of general formulas Cat[LnL]4, [LnL3Q] and [Ln(HL)3(NO3)3], where Cat+ = Cs+, NEt4+, PPh4 + and Q = 1,10-phenanthroline, 2,2-bipyridine or triphenylphosphine oxide, involving the use of thermal gravimetric analysis, X-ray analysis, and absorption and luminescence spectroscopy. We carried out a comparison with selected Ln3+ ß-diketonates. Possibilities and developments of theoretical calculations on energy transfer rates are also presented.
ABSTRACT
The caesium salt of dimethyl-N-benzoyl-amido-phosphate, namely, aqua-[di-meth-yl (N-benzoyl-amido-κO)phospho-nato-κO]caesium, [Cs(C9H11NO4P)(H2O)] or CsL·H2O, is reported. The compound crystallizes in the monoclinic crystal system in the P21/c space group and forms a mono-periodic polymeric structure due to the bridging function of the dimethyl-N-benzoyl-amido-phosphate anions towards the caesium cations.
ABSTRACT
The tetra-kis complex of neodymium(III), tetra-kis-{µ-N-[bis-(pyrrolidin-1-yl)phos-phor-yl]acet-am-id-ato}bis(pro-pan-2-ol)neodymiumsodium pro-pan-2-ol monosol-vate, [NaNd(C10H16Cl3N3O2)4(C3H8O)2]·C3H8O or NaNdPyr4(i-PrOH)2·i-PrOH, with the amide type CAPh ligand bis(N,N-tetra-methylene)(tri-chloro-acetyl)phos-phoric acid tri-amide (HPyr), has been synthesized, crystallized and characterized by X-ray diffraction. The complex does not have the tetra-kis-(CAPh)lanthanide anion, which is typical for ester-type CAPh-based coordin-ation compounds. Instead, the NdO8 polyhedron is formed by one oxygen atom of a 2-propanol mol-ecule and seven oxygen atoms of CAPh ligands in the title compound. Three CAPh ligands are coordinated in a bidentate chelating manner to the NdIII ion and simultaneously binding the sodium cation by µ2-bridging PO and CO groups while the fourth CAPh ligand is coordinated to the sodium cation in a bidentate chelating manner and, due to the µ2-bridging function of the PO group, also binds the neodymium ion.
ABSTRACT
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 â7 F4 transition, observed in the luminescence spectrum of NEt4 [EuL4 ], is discussed based on theoretical calculations.
Subject(s)
Lanthanoid Series Elements , Lanthanoid Series Elements/chemistry , Ligands , Luminescence , Magnetic Resonance Imaging , Magnetic Resonance SpectroscopyABSTRACT
The anionic tetra-kis-complex of lanthanum(III) NMe4LaL 4 with the CAPh-ligand dimethyl (2,2,2-tri-chloro-acet-yl)phospho-ramidate (HL), namely, tetra-methyl-ammonium tetra-kis-{2,2,2-tri-chloro-1-[(di-meth-oxy-phosphor-yl)imino]-ethano-lato}lanthanum(III), (C4H12N)[La(C4H6Cl3NO4P)4], has been synthesized, crystallized and structurally characterized by X-ray diffraction. The lanthanide ion is surrounded by four anionic, bis-chelating CAPh ligands forming the complex anion with a coordination number of eight for La3+ and NMe4 + as the counter-ion. The coordination polyhedron of the La3+ ion was inter-preted as a triangular dodeca-hedron.
ABSTRACT
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.
ABSTRACT
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-Hâ¯π inter-actions, forming chains along [001].
ABSTRACT
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 12.1â (1)-24.7â (1)°.