Quaternary Selenides EuLnCuSe(3): Synthesis, Structures, Properties and In Silico Studies

In this work, we report on the synthesis, in-depth crystal structure studies as well as optical and magnetic properties of newly synthesized heterometallic quaternary selenides of the Eu(+2)Ln(+3)Cu(+1)Se(3) composition. Crystal structures of the obtained compounds were refined by the derivative difference minimization (DDM) method from the powder X-ray diffraction data. The structures are found to belong to orthorhombic space groups Pnma (structure type Ba(2)MnS(3) for EuLaCuSe(3) and structure type Eu(2)CuS(3) for EuLnCuSe(3), where Ln = Sm, Gd, Tb, Dy, Ho and Y) and Cmcm (structure type KZrCuS(3) for EuLnCuSe(3), where Ln = Tm, Yb and Lu). Space groups Pnma and Cmcm were delimited based on the tolerance factor t’, and vibrational spectroscopy additionally confirmed the formation of three structural types. With a decrease in the ionic radius of Ln(3+) in the reported structures, the distortion of the (LnCuSe(3)) layers decreases, and a gradual formation of the more symmetric structure occurs in the sequence Ba(2)MnS(3) → Eu(2)CuS(3) → KZrCuS(3). According to magnetic studies, compounds EuLnCuSe(3) (Ln = Tb, Dy, Ho and Tm) each exhibit ferrimagnetic properties with transition temperatures ranging from 4.7 to 6.3 K. A negative magnetization effect is observed for compound EuHoCuSe(3) at temperatures below 4.8 K. The magnetic properties of the discussed selenides and isostructural sulfides were compared. The direct optical band gaps for EuLnCuSe(3), subtracted from the corresponding diffuse reflectance spectra, were found to be 1.87–2.09 eV. Deviation between experimental and calculated band gaps is ascribed to lower d states of Eu(2+) in the crystal field of EuLnCuSe(3), while anomalous narrowing of the band gap of EuYbCuSe(3) is explained by the low-lying charge-transfer state. Ab initio calculations of the crystal structures, elastic properties and phonon spectra of the reported compounds were performed.