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Drawbacks, such as low laser damage threshold (LDT), of existing IR nonlinear optical (NLO) materials necessitate the exploration of new candidates. Promising candidates should have been found in the Ba–In–Q (Q = S, Se) system close to the well-known IR NLO (Ba, Sr)–(Ga, Al)–Q system, but all known Ba–In–Q phases are centrosymmetric (CS), precluding them from being NLO-active. Two new chalcogenides, Ba13Zn7In12S38 (1) and Ba12Zn8In12Se38 (2), were obtained by the introduction of d10 Zn2+ in the Ba–In–Q (Q = S, Se) system, where mixing Zn2+ in In3+ sites resulted in non-centrosymmetric transformation. Their structures comprised rare impeller-like chalcogenide units containing four-membered tetrahedral cluster or T2-supertetrahedra blades. Remarkably, strong phase-matchable second harmonic generation efficiency (0.6 × AGS), high LDT (24 × AGS), wide IR transparency region, and congruent melting characteristic make 1 be a good candidate for high power IR-NLO applications. The current work provided an avenue to design IR NLO materials in NLO-active motifs containing CS chalcogenide systems by the incorporation of d10 metals. [ABSTRACT FROM AUTHOR]

Two new infrared (IR) nonlinear optical (NLO) chalcogenides, SrCdSnQ4 (Q = S and Se) (1 and 2), were obtained by mixing NLO-active metal chalcogenides and d10 metal tetrahedral motifs in an alkali metal-containing system. Their structures are constructed with edge- and corner-sharing CdQ4 and SnQ4 (Q = S and Se) units to form two-dimensional (CdSnQ4)2− layers, between which are embedded with Sr2+. Compounds 1 and 2 have moderate band gaps of 2.05 and 1.54 eV, respectively. They exhibit strong second-harmonic generation intensities that are comparable to that of the benchmark AgGaS2 using a 2040 nm laser. Furthermore, their laser-induced damage thresholds are 10 and 5 times higher than that of AgGaS2, respectively. The strong NLO efficiency of these two compounds can be ascribed to SnQ4 tetrahedra with a synergetic enhancement in the large distortion of CdQ4 tetrahedra, shedding light on the exploration of new IR NLO materials with mixed NLO-active and synergetic distorted motifs. [ABSTRACT FROM AUTHOR]

Two new inorganic supramolecular compounds, (Hg11P4)(GaCl4)4 (1) and (Hg3AsS)(GaCl4) (2), have been prepared by the solid-state reactions. Their structures are characterized by mercury-containing cationic hosts and discrete (GaCl4)− guests, which is a derivative of a very strong Lewis acid. The three-dimensional cationic framework of 1, (Hg11P4)4+, is marvellously extended by Hg22+ and Hg32+ groups as well as Hg2+ ions to form two large tunnels with different sizes each embedded with two columns of (GaCl4)− anions. Compound 2 features a layered structure with (GaCl4)− tetrahedra being intercalated between two-dimensional (Hg3AsS)+ layers and it is the first mercury pnictidechalcohalide. It is found that the weak electrostatic forces between hosts and guests play a key role in the stabilization of the whole structures of 1 and 2, which is strikingly different from almost all the reported metal pnictidehalide and chalcohalide supramolecular compounds. Optical dielectric constants calculations show that both 1 and 2 possess strong dielectric anisotropy. [ABSTRACT FROM AUTHOR]

A novel chiral open-framework structural hexanary chalcogenoborate, (K3I)[SmB12(GaS4)3] (1), was obtained by a facile approach using boron as the reducing reagent; it shows weak SHG-activity and is transparent in the mid-IR region. [ABSTRACT FROM AUTHOR]

Two new inorganic supramolecular compounds, (Hg11P4)(GaCl4)4 (1) and (Hg3AsS)(GaCl4) (2), have been prepared by the solid-state reactions. Their structures are characterized by mercury-containing cationic hosts and discrete (GaCl4)− guests, which is a derivative of a very strong Lewis acid. The three-dimensional cationic framework of 1, (Hg11P4)4+, is marvellously extended by Hg22+ and Hg32+ groups as well as Hg2+ ions to form two large tunnels with different sizes each embedded with two columns of (GaCl4)− anions. Compound 2 features a layered structure with (GaCl4)− tetrahedra being intercalated between two-dimensional (Hg3AsS)+ layers and it is the first mercury pnictidechalcohalide. It is found that the weak electrostatic forces between hosts and guests play a key role in the stabilization of the whole structures of 1 and 2, which is strikingly different from almost all the reported metal pnictidehalide and chalcohalide supramolecular compounds. Optical dielectric constants calculations show that both 1 and 2 possess strong dielectric anisotropy. [ABSTRACT FROM AUTHOR]

Mid-far infrared (IR) non-linear optical (NLO) materials are of great importance in military and civil fields. However, commercial IR-NLO crystals (such as AgGaS 2 , AgGaSe 2 and ZnGeP 2 ) do not currently satisfy the requirements of large second-harmonic generation (SHG) and high laser induced damage thresholds (LIDTs), which seriously limits their practical applications. Herein, we have developed a new series of salt-inclusion chalcogenides, [A 3 X][Ga 3 PS 8 ] (A = K, Rb; X = Cl, Br), which are constructed from alternate stacking of adamantane-like [Ga 3 PS 10 ] 6- cluster layers and cationic [A 3 X] 2+ salt layers. Importantly, they display both large SHG responses of several-fold and high LIDTs for dozens of times that of commercial AgGaS 2 , which exhibit the highest LIDTs among the reported IR-NLO materials with a larger SHG conversion efficiency than that of AgGaS 2 . These properties together with wide transparent region, type I phase-matching features and congruent-melting behaviors indicate they are promising IR-NLO materials.

Two new inorganic supramolecular compounds, (Hg11P4)(GaCl4)4 (1) and (Hg3AsS)(GaCl4) (2), have been prepared by the solid-state reactions. Their structures are characterized by mercury-containing cationic hosts and discrete (GaCl4)(-) guests, which is a derivative of a very strong Lewis acid. The three-dimensional cationic framework of 1, (Hg11P4)(4+), is marvellously extended by Hg2(2+) and Hg3(2+) groups as well as Hg(2+) ions to form two large tunnels with different sizes each embedded with two columns of (GaCl4)(-) anions. Compound 2 features a layered structure with (GaCl4)(-) tetrahedra being intercalated between two-dimensional (Hg3AsS)(+) layers and it is the first mercury pnictidechalcohalide. It is found that the weak electrostatic forces between hosts and guests play a key role in the stabilization of the whole structures of 1 and 2, which is strikingly different from almost all the reported metal pnictidehalide and chalcohalide supramolecular compounds. Optical dielectric constants calculations show that both 1 and 2 possess strong dielectric anisotropy.