Novel structural transformation in K3ReP2S8 thiophosphates originating from the rare-earth (Re) cation sizes induced local coordination asymmetry

Na6Sn3P4S16: Sn(ii)-chelated PS4 groups inspired an ultra-strong SHG response

“…The experimental Raman spectrum measured under 532 nm laser radiation indicates that the Raman peaks (410-584 cm −1 ) can also be attributed to the same characteristic absorption of the P-S bonding mode (Fig. 4d) as for Hg 3 P 2 S 8 34 (360-600 cm −1 ) and K 3 ReP 2 S 8 45 (400-600 cm −1 ).…”

“…1a). [34][35][36][37][40][41][42][43][44][45][46][47][48][49][50][51] Compared with known SnPS 3 , 52 Na 6 Sn 3 P 4 S 16 also shows an obvious improvement in bandgap and SHG effect (Fig. 1b), illustrating the importance of the Sn(II)S 4 unit for material performance.…”

Low temperature molten salt synthesis of noncentrosymmetric (NH4)3SbF3(NO3)3and centrosymmetric (NH4)3SbF4(NO3)2

“…It is well known that the primary characteristic of a NLO crystalline material is that it has a noncentrosymmetric (NCS) structure; that is, the compound must crystallize in a noncentrosymmetric space group. 11,12 It has been found that the reasonable combination of different asymmetric chromo-phores is an effective tactic for the synthesis of NLO materials, which is conducive to the generation of large second harmonic generation (SHG) response. 13,14 Common asymmetric chromophores include (1) planar π-conjugated anions, such as BO 3 3− , CO 3 2− , and NO 3 − ; [15][16][17] (2) distorted polyhedra of d 0 and d 10 transition metal ions, such as Ti 4+ , Mo 6+ , Zn 2+ , and Hg 2+ ; [18][19][20][21][22] (3) lone pair electron cations with stereochemical activity, such as Pb 2+ and Bi 3+ .…”

Noncentrosymmetric Na6Pb3P4S16 and Centrosymmetric K2MIIP2S6 (MII = Mg and Zn) Displaying Multiple Membered-Ring Configurations and Strong Optical Anisotropy

“…In recent years, metal thiophosphates have attracted extensive research interest due to the diverse structures and flexible composition types, which can provide more opportunities for the design and synthesis of new multifunctional materials. − The P element has multiple valence states (+5 and +4) and link with S atoms to form various [P x S y ] n ‑ anionic groups, such as [PS 4 ] 3– , ethane-like [P 2 S 6 ] 4– , coedge [P 2 S 6 ] 2– , cocorner [P 2 S 7 ] 4– , [P 3 S 9 ] 3– trimer, [P 3 S 10 ] 5– cluster, etc., which could further modulate the physicochemical properties of thiophosphates and bring about the extensive applications, , such as ionic conductivity, − catalysis, , photoluminescence, ,, ferroelectricity, and thermoelectricity. − For instance, Li 4 P 2 S 6 and Li 3 PS 4 were established as solid electrolyte materials; − Sn 2 P 2 S 6 was proven as an excellent ferroelectric material; MPS 3 (M = transition metal) compounds were studied as potential electrode materials for the application in high-energy density batteries. − Furthermore, thiophosphates are of important research systems in the exploration of promising infrared nonlinear optical (IR NLO) crystals with strong second harmonic generation (SHG) response, proper birefringence (Δ n ), and broad bandgap. − Their covalent P–S bonds not only produce the significant NLO effect but also exhibit wide short-wave transmittance, which enables the thiophosphates to achieve a balance between wide bandgap and large SHG effect. − In addition, birefringent materials can modulate the polarization of light that is indispensable to the rapid development of laser industry. , The great anisotropy of ethane-like [P 2 S 6 ] dimers may lead to large birefringence. , As we know, cations with stereochemically active...…”