Low-Frequency Sub-Terahertz Absorption in HgII -XCN-FeII (X=S, Se) Coordination Polymers.

Self-assembly FeII complexes of phenazine (Phen), quinoxaline (Qxn), and 4,4'-trimethylenedipyridine (Tmp) with tetrahedral building blocks of [HgII (XCN)4 ]2- (X=S or Se) formed six new high-dimensional frameworks with the general formula of [Fe(L)m ][Hg(XCN)4 ]⋅solvents (L=Phen, m/X=2/S, 1; L=Qxn, m/X=2/S, 2; L=Qxn, m/X=1/S, 3; L=Qxn, m/X=1/Se, 3-Se; L=Tmp, m/X=1/S, 4; and L=Tmp, m/X=1/Se, 4-Se). 1, 3, and 3-Se show an intense sub-terahertz (sub-THz) absorbance of around 0.60 THz due to vibrations of the solvent molecules coordinated to the FeII ions and crystallization organic molecules. In addition, crystals of 1, 4, and 4-Se display low-frequency Raman scattering with exceptionally low values of 0.44, 0.51, and 0.53 THz, respectively. These results indicate that heavy metal FeII -HgII systems are promising platforms to construct sub-THz absorbers.

Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence.

Molecular vibrations in the solid-state, detectable in the terahertz (THz) region, are the subject of research to further develop THz technologies. To observe such vibrations in terahertz time-domain spectroscopy (THz-TDS) and low-frequency (LF) Raman spectroscopy, two supramolecular assemblies with the formula [NdIII (phen)3 (NCX)3] 0.3EtOH (X = S, 1-S; Se, 1-Se) were designed and prepared. Both compounds show several THz-TDS and LF-Raman peaks in the sub-THz range, with the lowest frequencies of 0.65 and 0.59 THz for 1-S and 1-Se, and 0.75 and 0.61 THz for 1-S and 1-Se, respectively. The peak redshift was observed due to the substitution of SCN- by SeCN-. Additionally, temperature-dependent TDS-THz studies showed a thermal blueshift phenomenon, as the peak position shifted to 0.68 THz for 1-S and 0.62 THz for 1-Se at 10 K. Based on ab initio calculations, sub-THz vibrations were ascribed to the swaying of the three thiocyanate/selenocyanate. Moreover, both samples exhibited near-infrared (NIR) emission from Nd (III), and very good thermometric properties in the 300-150 K range, comparable to neodymium (III) oxide-based thermometers and higher than previously reported complexes. Moreover, the temperature dependence of fluorescence and THz spectroscopy analysis showed that the reduction in anharmonic thermal vibrations leads to a significant increase in the intensity and a reduction in the width of the emission and LF absorption peaks. These studies provide the basis for developing new routes to adjust the LF vibrational absorption.