Complexes of (2-methyl-4-oxopent-2-yl)diphenylphosphine oxide with uranyl and neodymium nitrates: synthesis and structures in the solid state and in solution

Synthesis and Coordination Properties of Tripodal Ligand on the Triphenylphosphine Oxide Platform with Carbamoyl Side Arms

“…Typical decrease in ν P O on coordination of phosphoryl-containing ligands in complexes with uranyl and lanthanide nitrates is 30-50 cm −1 . [31][32][33][34] The bands of ν C O change: a weak band remains in the region of vibrations of free C O groups (1664 cm −1 ) and a strong band appears at 1601 cm −1 that corresponds to vibrations of coordinated groups. One can suppose, taking into account intensity ratio, that two C O groups are coordinated in complex 3, while one group remains free.…”

“…33,37,38 Signal broadening in the 31 P NMR spectra of uranyl complexes with phosphoryl ligands is usually insignificant (10-20 Hz) because uranium(VI) cation is Downloaded by [Florida State University] at 07:49 01 November 2014 diamagnetic. The considerable broadening of the NMR signals in the spectrum of complex 3 seems to indicate slow exchange processes within the same molecule or the existence of several forms of complexes.…”

“…42 We believe as well that the formation of fork-like hydrogen bond between the H atom of the coordinated water molecule and the coordinated phosphoryl oxygen is most likely because the reduction of ν(P O) upon the formation of uranyl complex 3 is much larger than that usually observed in the complexes with uranyl nitrate. 33 43 Only two structures with nine-coordinated U(VI) are presented in CCDC and ICSD, one of bidentate anions is arranged perpendicularly to the equatorial plane in both structures. 44 The signals in 31 P{ 1 H} and 1 H NMR spectra of neodimium complex 4 are considerably broadened, which is explained by both paramagnetic properties of the cation and possibly slow exchange processes between several complex forms.…”

Phosphine Oxide-Nd3+ Coordination Chains with Cumulated Output Enable Efficient LED-Pumping Optical Amplification

“…In this sense, one-dimensional (1D) coordination chains with appropriately concentrated Nd 3+ units would be “ideal” if interchain interaction can be effectively suppressed. Actually, the coordination spheres of Nd 3+ should keep stable during device fabrication, and therefore ligands with strong coordination abilities, e.g., β-diketone and phosphine oxide, are desired for enhancing processability. , However, except for a nonprocessable Nd-MOF, all reported Nd 3+ complexes containing β-diketone and phosphine oxide ligands were mononuclear until present. − Nd 3+ coordination polymers with well-defined structures were absent, let alone lanthanide coordination polymer-based RDWAs. It is already demonstrated that aromatic ligands can effectively improve absorption ability of the complexes. − Especially, rigid phosphine oxide ligands markedly enhanced NIR emissions of mononuclear Nd 3+ complexes through alleviating low-frequency vibration-induced energy loss, in addition to their tunable energy levels well matching with those of primary ligands and Nd 3+ ions. , Nonetheless, with respect to developing high-performance Nd 3+ coordination polymers, excited-state quenching by vibrational de-excitation and interpolymer interactions should be simultaneously suppressed through enhancing both ligand molecular and coordination rigidities.…”

Effect of the nature of substituents at the phosphorus atom on extraction properties of phosphorylketones toward f-elements

“…11, November, 2014 dicate, as a rule, a monodentate* P(O) coordination of the ligand. [15][16][17] However, the presence of the C(O) group in the alkyl substituent improves extraction properties of the compound (diphenylphosphorylated ketone) as com pared to the model phosphine oxide. 12, 13 Variation of sub stituent at the P(O) group of the ligand changes its affinity to the metal cation and its efficiency and selectivity as an extractant, since this changes basicity of the coordination center (and, therefore, stability of the complex), complex composition, and lipophilicity of both components, the ligand and the extracting complex.…”