New Light on an Old Story: The Crystal Structure of Boron Tetrathiophosphate Revisited

Abstract

The crystal structure of boron tetrathiophosphate BPS 4 was reinvestigated using single-crystal X-ray diffraction. The structure shows unidimensional chains similar to SiS 2 as structural motifs. BPS 4 crystallizes in the orthorhombic space group Ibam (no. 72), with a = 5.6173 (3), b = 8.9929(4), c = 5.2433(3) Å and V = 264.87(2) Å 3 and is closely related to the orthorhombic high-temperature modification of AlPS 4 (ht-AlPS 4 ). The SiS 2 -like chains are all oriented parallel to the c axis, which explains the needle-like morphology and that the * Prof. Dr. B. V. Lotsch E-Mail: b.lotsch@fkf.mpg.de [a] Zeitschrift für anorganische und allgemeine Chemie ARTICLE forming the single-crystal Raman scattering, M.-L. Schreiber for ICP-OES analyses, F. Falkenberg for the high-pressure treatments and the Computer Service group at MPI-FKF for providing computational facilities.

First-Principles Design and Simulations Promote the Development of Nonlinear Optical Crystals

“…Based on the in-depth understanding of MIR NLO structure–property relations, a large number of subsequent experiments were performed, both verifying our theoretical insights and realizing some NLO structures with balanced performances. In particular, our first-principles studies made thiophosphates “receive significant attention more than 125 years after their discovery” . Under this guidance, Zn 3 (PS 4 ) 2 , LiZnPS 4 , and AgZnPS 4 have been synthesized ,, and the experimental measurements are in agreement with our theoretical predictions.…”

“…Accordingly, considerable structures have been proposed as promising MIR NLO material candidates in thiophosphates, halides, oxides, and diamond-like chalcogenides. Some of them have been experimentally confirmed and lead the “new light on an old story” …”

Lanthanide orthothiophosphates revisited: single-crystal X-ray, Raman, and DFT studies of TmPS4 and YbPS4

“…Upon heating we observed only one endothermic peak for both lanthanides, namely, at T = 1363 K for TmPS 4 and at 1305 K for YbPS 4 . Upon cooling, TmPS 4 solidifies at 1353 K while YbPS 4 was slightly subcooled to 1278 K. Comparison with the thermal behavior of other orthothiophosphates studied previously suggests that TmPS 4 and YbPS 4 have a particularly high thermal stability: For example, K 2 AuPS 4 and Tl 2 AuPS 4 melt congruently already around 660-690 K [24], BPS 4 melts congruently at 780 K [3], and Ag 3 PS 4 melts incongruently at 800 K [25]. High melting points are also found in ht-AlPS 4 (1070 K) [2] and Cu 3 PS 4 (1240 K) [26].…”

“…A multitude of ternary compounds based on the orthothiophosphate anion [PS 4 ] 3− has been reported over the last decades, and they continue to receive significant attention owing to their varied materials properties, even more than 125 years after their discovery [1][2][3][4][5][6][7][8][9][10][11]. The first compound, SbPS 4 , was reported by Glatzel in 1891 [12], followed 2 years later by a comprehensive study on "Normale Sulfophosphate", describing their properties and syntheses [13].…”

Hg3P2S8: A New Promising Infrared Nonlinear Optical Material with a Large Second-Harmonic Generation and a High Laser-Induced Damage Threshold

“…The defective DLS compounds (Figure S1) can be viewed as a variation from the ordinary DLS. , When the monovalent A-site elements like Li, Cu, and Ag in the ordinary DLS are replaced by multivalent elements (d 10 metals or IIIA group elements), cation vacancies will be generated in the compound to maintain the charge balance. Compared with the ordinary DLS, the NLO-active MQ 4 (M = d 10 metals or IIIA group elements, Q = S and Se) units tend to form stronger covalent bonds and produce more flexible and distorted tetrahedral geometries in the defective DLS compound, which is favorable to producing a strong SHG effect. Based on the aliovalent element substitution, several defective DLS chalcogenide compounds with stronger SHG responses and larger band gaps than the benchmark AGS, like InPS 4 , , Zn 3 P 2 S 8 , , and HgGa 2 S 4 , , have been discovered.…”