First examples of carbacylamidophosphate pentanuclear hydroxo-complexes: Synthesis, structure, luminescence and magnetic properties

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

“…Later we noticed that in the case of heavy lanthanides the formation of such hydroxo species was inherent and arbitrarily happened as a concurrent reaction during the synthesis of LnL 3 bipy (Ln III = Dy–Yb) complexes . We did not find any signs of SMM behavior for Tb 5 L 6 (μ-L) 4 (μ 3 -OH) 4 (μ 4 -OH) at T = 2 K and above and an ac magnetic field frequency up to 1.5 kHz, though the occurrence of at least a nonzero out-of-phase signal for this compound could be expected. , …”

“…Compounds 2 – 5 were synthesized as described previously . The only difference from the reported method was in the case of 1 , where stirring of the suspension of the precipitated hydrated ternary neodymium complex in water at 70 °C for 30 min was required to complete the hydrolysis reaction.…”

“…This work is an extension of our study of hydroxo-bridged lanthanide coordination compounds with a carbacylamidophosphate (CAPh) type liganddimethyl N -benzoylamidophosphate (HL, Figure ). Recently we have found that the reaction of Ln III salts with dimethyl N -benzoylamidophosphate led to unexpected self-arrangement of the pentanuclear cores Ln 5 L 6 (μ-L) 4 (μ 3 -OH) 4 (μ 4 -OH) (Ln III = Gd, Eu, Tb) . It was shown that the Eu III and Tb III complexes demonstrated strong emission in spite of the presence of hydroxo groupsknown luminescence quenchers .…”

Spectroscopy and structure of [LnL3bipy] and [LnL3phen] complexes with CAPh type ligand dimethylbenzoylamidophosphate

“…The crystals were separated by fil- The procedure of preparation of [LnL 3 bipy] complexes has the single difference, when instead of 1,10-phenantroline (1 mmol), 2,2 0 -bipyridine (1.2 mmol) was added on the last stage of the synthesis. The 20% excess of 2,2 0 -bipyridine is necessary in case of obtaining complexes with metals of the second part of lanthanides row because of the complexes partial hydrolysis with formation of hydroxo-species [29]. Yields of [LnL 3 bipy] complexes for such lanthanides as La-Nd, Sm-Tb were equal to $ 85-90%, for complexes with lanthanide ions of the end of the row (Ln¼ Dy-Yb) yields were lower and equal $60%, because of co-product formation.…”

1H- and 31P-NMR Spectroscopy Study of Paramagnetic Lanthanide Coordination Compounds [LnL3 • Phen] (L = CCl3C(O)NP(O)(OCH3)2)

“…A particular advantage of the CAPh compounds with respect to other chelating oxygen-donor ligands -e.g., -diketones [8] -consists in the presence of phosphorus atoms in the CAPh ligand composition, which are known to be a convenient 31 P-NMR probe. A high affinity of those ligands to lanthanide (III) ions, a synthetic possibility of introducing substituents, different in their steric characteristics and electron structures, near the functional chelating fragment −C(O)N(H)P(O)= led to a systematic study of lanthanide complexes with CAPh ligands [9][10][11][12][13][14][15].…”