3848-53-1Relevant academic research and scientific papers
Imidodiphosphonate ligands for enhanced sensitization and shielding of visible and near-infrared lanthanides
Davis, Dita,Carrod, Andrew J.,Guo, Zhilin,Kariuki, Benson M.,Zhang, Yuan-Zhu,Pikramenou, Zoe
, p. 13268 - 13275 (2019)
The design of coordination sites around lanthanide ions has a strong impact on the sensitization of their luminescent signal. An imidodiphosphonate anionic binding site is attractive as it can be functionalized with "remote" sensitizer units, such as phenoxy moieties, namely, HtpOp, accompanied by an increased distance of the lanthanide from the ligand high-energy stretching vibrations which quench the luminescence signal, hence providing flexible shielding of the lanthanide. We report the formation and isolation of Ln(tpOp)3 complexes where Ln = Er, Gd, Tb, Dy, Eu, and Yb and the Y(tpOp)3 diamagnetic analogue. The complexes are formed from reaction of KtpOp and the corresponding LnCl3·6H2O salt either by titration and in situ formation or by mixing and isolation. All complexes are seven-coordinated by three tpOp ligand plus one ethanol molecule, except for Yb(tpOp)3 which has no solvent coordinated. Phosphorus NMR shows characteristic shifts to support the coordination of the lanthanide complexes. The complexes display visible and near-infrared luminescence with long lifetimes even for the near-infrared complexes which range from 3.3 μs for Nd(tpOp)3 to 20 μs for Yb(tpOp)3. The ligand shows more efficient sensitization than the imidodiphosphinate analogues for all lanthanide complexes with a notable quantum yield of the Tb(tpOp)3 complex at 45%. We attribute this to the properties of the remote sensitizer unit and its positioning further away from the lanthanide, eliminating quenching of high energy C-H vibrations from the ligand shell. Calculations of the ligand shielding support the photophysical properties of the complexes. These results suggest that these binding sites are promising in the further development of the lanthanide complexes in optoelectronic devices for telecommunications and new light emitting materials.
Interaction in molecular crystals, 156 [1, 2]. Crystal growth and structure determination of alkali(imidodiphosphate) salts with cations of low and high coordination numbers
Bock, Hans,Heigel, Erik,Nagel, Norbert
, p. 773 - 784 (2000)
Imidodiphosphates ?N[PO(OR)2]2 and Imidodiphosphonates ?N[POR2]2 are effective chelating ligands for a variety of metal cations including even Na⊕ for which a lipophilically wrapped hexameric polyion cluster has been structurally characterized. The corresponding hexameric lithium and polyrubidium ion complexes reported here exhibit considerable structural differences: The rather small Li⊕ cations of coordination number five and tetraphenylimidodiphosphate form an isolated hexameric aggregate analogous to the Na⊕ one, whereas the larger Rb⊕ with coordination number seven and (3,4-dimethylphenyl)substituents crystallizes as a chain polymer. Based on the crystal structures, the dominant Coulomb attractions between cations and anions, the spatial requirement of the ligands and the essential phenyl/phenyl interactions in their lipophilic skin are discussed. Lipophilically Wrapped Polylithium-and Polyrubidium-Ionclusters, Imidodiphosphate Ligands.
Synthesis of Acyl Phosphoramidates Employing a Modified Staudinger Reaction
Currie, Iain,Sleebs, Brad E.
supporting information, p. 464 - 468 (2021/02/03)
A one-step synthesis of acyl phosphoramidates from a variety of functionalized acyl azides has been developed employing trimethylsilyl chloride as an activating agent in a modified Staudinger reaction. The methodology was further adapted to include the in situ generation of the acyl azides from a diverse selection of carboxylic acids and hydrazide starting synthons. The reaction scope was extended to include the synthesis of imidodiphosphates and the natural product Microcin C.
Synthesis of novel bisphosphorylimides based on Staudinger reaction
D?ring, Manfred,Fuhr, Olaf,Goedderz, Daniela,Weber, Lais,Weinert, Michael
, (2020/09/07)
A series of bisphosphorylimides based on the reaction sequence of Atherton-Todd and Staudinger reaction were synthesized. These bisphosphorylimides containing phosphorus in different chemical environments, while the reaction sequence is using mild conditions and moreover can be synthesized in an one-pot procedure. The molecular structures were revealed by nuclear magnetic resonance spectroscopy and x-ray crystallography. The stability of the bisphosphorylimides against hydrolysis and thermal influences was tested which allows an initial estimation about the usage as flame retardant.
Reaction of Imidodiphosphoric Tetraphenylester with Mercury(II) Oxide and Phenylmercuryhydroxide
Richter, Horst,Fluck, Ekkehard,Schwarz, Wolfgang
, p. 578 - 583 (2007/10/02)
Reaction of Imidodiphosphoric tetraphenylester with HgO yields the twelve membered ring system 1, the properties, NMR and X-ray structural data of which are reported.A reaction mechanism is suggested.Reaction product from imidodiphosphoric tetraphenylester and C6H5HgOH is N-phenylmercury-bis(phosphoric diphenylester)-imide (2). - Keywords: Imidodiphosphoric Tetraphenylester, Diazadiphosphadimercuracyclododecin
The formation of P-N and P-N-P bonds by elimination of phenol in a basic condensation
Nielsen, Morris L.
, p. 1760 - 1767 (2008/10/08)
Displacement of phenol from a phenyl ester of phosphoric acid or a phosphoramidic acid by anions of certain amines or phosphoramidates in the presence of a base results in the formation of P-N and P-N-P bonds. From (C6H5O)3PO and NaNHC6H5 there was obtained (C6H5O)2P(O)NHC6H5; with NaN(C6H5)2, the product was (C6H5O)2P(O)N(C6H5) 2. From (C6H5O)3PO and sodium amide, however, the product was (C6H5O)2P(O)NHP(O)(OC6H 5)2. From (C6H5O)2P(O)NH2, by self-condensation, was obtained both (C6H5O)2P(O)NHP(O)(OC6H 5)NH2 and (C6H5O)2(O)NHP(O)(OC6H 5)NHP(O)(OC6H5)NH2. From (C6H5O)3PO and (C6H5O)2P(O)NH2 the principal product was (C6H5O)2P(O)NHP(O)(OC6H 5)NHP(O)(OC6H5)2. The last three compounds have not been reported before. The properties of these compounds and their metal and amine derivatives are described.
