SYNTHESIS AND SPECTRAL INVESTIGATIONS OF ANIONIC NaLnL4 AND NEUTRAL MIXED-LIGAND (LnL3phen, LnL3bipy) LANTHANIDE (III) COMPLEXES BASED ON O,O′-DIMETHYL-N-(3-NITROBENZOYL)AMIDOPHOSPHATE
DOI: https://doi.org/10.17721/1728-2209.2025.1(60).6
Keywords:
carbacylamidophosphate, lanthanides, tetrakis complexes, mixed-ligand complexes, spectroscopyAbstract
Background. Lanthanide complexes Ln3+ play an important role in the development of advanced technologies due to their unique photophysical properties, which leads to a constant expansion of their application, from being part of functional metal-organic frameworks (MOFs) for sensor technology and catalysis and components of hybrid materials for optoelectronics to highly sensitive luminescent thermometers that allow temperature measurement in the micro- and nanoscale ranges. The implementation of such properties requires the use of lanthanide complexes Ln3+ with highly efficient “antenna” ligands. Among the promising phosphors, lanthanide complexes Ln3+ based on carbacylamidophosphates (CAPH ligands) can be distinguished, since the presence of P=O and C=O donor groups in their structure provides high affinity to Ln³⁺ ions with the possibility of chelate coordination through oxygen atoms to form stable six-membered metal cycles.
The aim of this work was to investigate the possibility of forming mono- and hetero-ligand complexes of lanthanides with O,O′-dimethyl-N-(3-nitrobenzoyl)amidophosphate, as well as to study and compare their properties.
Methods. The complexes were synthesized using standard methods based on the exchange reaction between lanthanide nitrate and sodium salts of the ligand in non-aqueous solutions. Methods of infrared, electronic, 1H, and 31P NMR spectroscopies were used to investigate the composition and structure of the synthesized complexes.
Results. On the basis of results of the investigation by IR spectroscopy, it was established that the CAPh ligand coordinates to the lanthanide ion in a deprotonated state bidentate-chelate via the oxygen atoms of the carbonyl and phosphoryl groups. Based on the date of 1H NMR spectroscopy of lanthanum complexes, the inclusion of the CAPh ligand in the coordination sphere in a deprotonated state was confirmed, and it was also proved that the ratio of CAPh and additional ligands in neutral complexes corresponds to the proposed (3:1). Analysis of the electronic spectra of Nd3+ complexes in the 4I9/2→4G5/2, 2G7/2 transition region confirms the realization of the coordination number of the central ion 8.
Сonclusions. The new coordination compounds of lanthanides (III) with the following chemical formulas: Na[LnL4], LnL3phen, LnL3bipy, where Ln = La, Nd, Eu, Tb, Er; HL – O,O -dimethyl-N-(3-nitrobenzoyl)amidophosphate; phen – 1,10-phenanthroline; bipy – α,α'-bipyridine were successfully synthesized. The conclusions about bidentate coordination of ligands to the central atom with the realization of the central ion's coordination number 8 were made based on IR, electronic, 31P NMR, and 1H NMR spectroscopy.
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