Two Related Gadolinium Aquo Carbonate 2-D and 3-D Structures and Their Thermal, Spectroscopic, and Paramagnetic Properties

Abstract

We report two new extended inorganic materials based on gadolinium. The first, [Gd(CO(3))(2)H(2)O][NH(4)], consists of negatively charged 2-D sheets of gadolinium carbonate with one coordinated water molecule and an ammonium cation between the layers. The coordinated water and one carbonate extend into the interlayer space, connecting the layers via an extensive hydrogen bonding network which includes the ammonium ions. The second, a closely related yet more condensed framework structure, [Gd(2)(CO(3))(3)NH(3)H(2)O], is formed at a higher hydrothermal temperature and was characterized by single crystal X-ray diffraction data collected at a synchrotron. This second structure contains layers that are isostructural to the first, bridged together by carbonate, and coordinated by water and ammonia. The properties of these materials were studied by thermogravimetric analysis-mass spectrometry, photoluminescence, electron paramagnetic resonance, and Raman and infrared spectroscopy. The 2-D [Gd(CO(3))(2)H(2)O][NH(4)] is stable to about 175 degrees C, though water and ammonium loss continues through the entire thermogravimetric analysis trace. The 3-D material remains intact until about 325 degrees C. Both structures exhibit broad luminescence bands in the near-ultraviolet region centered at 354 nm. Electron paramagnetic resonance and magnetic susceptibility show spin-spin coupling between adjacent gadolinium atoms in both structures and confirm that they are paramagnetic. These materials show interesting photoluminescent and paramagnetic properties that could possibly be exploited for chemical sensing or magnetic materials applications.

Preparation of N,N-Dialkylcarbamato Lanthanide Complexes by Extraction of Lanthanide Ions from Aqueous Solution into Hydrocarbons

“…The carbonato ligand makes with the four metal atoms four shorter bonds and two longer ones, namely O(1)–Tb(4) and O(3)–Tb(3). A similar coordination of the carbonato group has been described in several polynuclear lanthanide derivatives . The carbonato plane is tilted with respect to the plane of the metal atoms.…”

Glycol modified gadolinium oxide nanoparticles as a potential template for selective and sensitive detection of 4-nitrophenol

“…The corresponding asymmetry factor was calculated from the full width at half maxima (FWHM) around the main peak. 32 On interpretation, it has been found that the FWHM values varied as a function of surface capping. The increased FWHM value further corresponds to the enhancement of defect related emission as compared to band-to-band emission in Gd 2 O 3 nanoparticles.…”

“…This broad peak with maxima in the vicinity of 350 nm has been corresponded to 6 P 7/2 2 8 S 7/2 of Gd(III). 32 Additionally the nature of the surface covering also influenced the surface defects in the Gd 2 O 3 nanoparticles which further affect the asymmetry in the PL spectra for the surface capped Gd 2 O 3 nanoparticles. Moreover higher PL intensities in each case pointed towards the minor loss of photo generated carriers via non-radiative recombination.…”

Lanthanide−Organic Framework of a Rigid Bis-Gd Complex: Composed by Carbonate Ions Spacers

“…Although metal carbonates have been well studied, thus far there are only a few metal and lanthanide carbonate networks known, and the carbonate ions were used as building blocks . We are not aware of systems in which carbonate anions function as spacers of metallo-organic coordination complexes to create a MOF.…”