Inorganic Supramolecular Compounds with 3-D Chiral Frameworks Show Potential as Both Mid-IR Second-Order Nonlinear Optical and Piezoelectric Materials

Abstract

Two inorganic supramolecular compounds, (Hg(6)P(3))(In(2)Cl(9)) (1) and (Hg(8)As(4))(Bi(3)Cl(13)) (2), which have chiral 3-D host frameworks with guest moieties filling the helical tunnels, have been synthesized. They both have large second-harmonic generation efficiencies, and compound 2 also exhibits obvious single-crystal piezoelectric performance. Theoretical studies from first-principles calculations were performed on their nonlinear optical (NLO) and piezoelectric properties, and results indicate that good NLO and piezoelectric materials can be obtained by designing both complicated polycations and polyanions with large molecular polarizability as functional components rather than traditional single polyanions.

Auxiliary ligand-assisted two novel one-dimensional indium coordination polymers: Synthesis, crystal structures and photoluminescence characterization effected by solvent and temperature

“…36(8)°. The In-Cl distance is 2.400(8) Å, which lies in the normal bond length ranges reported previously [32]. The adjacent 1,4-bda 2 − are nearly coplanar with the dihedral angle of 8.63°.…”

Synthesis, crystal structure and second-order nonlinear optical property of a novel pentanary selenide (K3I)[InB12(InSe4)3]

“…(1) Metal chalcogenides, mainly ternary or quaternary materials, such as ZnY 6 Si 2 S 14 , 4 A 4 GeP 4 Q 12 (A = K, Rb, Cs; Q = S, Se), 5 AX II 4 X III 5 Se 12 (A = K + -Cs + ; X II = Mn 2+ , Cd 2+ ; X III = Ga 3+ , In 3+ ), 6 Ba 6 Sn 6 Se 13 , 7 Ba 8 Sn 4 S 15 ; 8 (2) metal pnictides, such as CdSiP 2 and ZnGeP 2 ; 9 (3) metal halides, such as Rb 2 CdBr 2 I 2 ; 10 (4) metal halates or halides, such as K(VO) 2 O 2 (IO 3 ) 3 11, 12 and Pb 17 O 8 Cl 18 ; 13 (5) different bond-type hybrid compounds, such as NaBa 4-Ge 3 S 10 Cl, 14 (Hg 6 P 3 )(In 2 Cl 9 ) and (Hg 8 As 4 )(Bi 3 Cl 13 ). 15 Combining the social demand and our group's rich experiences in synthesizing multinary metal chalcogenides, 16 we started to explore new chalcogenide-type IR second-order NLO materials several years ago, and several chalcogenides with good SHG effects and large ALDT were discovered. 4,16,17 In the present work, (K 3 I)[InB 12 (InSe 4 ) 3 ], a novel pentanary selenide featuring InSe 4 tetrahedra consolidated by B 12 Se 12 clusters, was obtained by modified high-temperature solid-state reaction.…”

Five hybrid thiocyanate networks oriented by polyvalent cationic templates: Synthesis, structure and properties

“…(Generally, a dramatic structural change in volume, rigidity, charge, symmetry of the basic inorganic phases can be reached by introduction of new organic templates called structural directing agents (SDAs) [8][9][10][11]) Although rich research in the host-guest chemistry of hybrids oriented by monocations and dications, the use of multications to fabricate multidimensional and hierarchical self-assemblies are rarely reported [12][13][14].…”