l-Homoproline-Directed Synthesis of Organic-Inorganic Metal Iodides for Second Harmonic Generation.

Three organic-inorganic metal iodides, namely, (NH4)(l-hp)ZnI3 (1), [Cd(l-hp)4]Cd3I8 (2), and (l-Hhp)(l-hp)PbI3 (3), have been synthesized using l-homoproline (l-hp) as the structure-directing agent. These compounds feature different noncentrosymmetric structures and optical properties. In particular, compound 3 shows a large second-harmonic-generation response of 3.4 times that of KH2PO4. Density functional theory calculations were performed to gain insight into its structure-property relationship.

Multiple Functions of l-Thioproline in the Synthesis of Chiral Metal Bromides Showing Second-Harmonic-Generation Responses.

Three new homochiral metal bromides, namely, (l-Htp)2Cu2Br4 (1), (l-Htp)(l-tp)CdBr3 (2), and (l-tp)2ZnBr2 (3), were prepared using l-thioproline as the chiral template. These compounds feature dimeric, chainlike, and monomeric structures. Their second-harmonic-generation (SHG) efficiencies are 0.1, 0.3, and 2.0 times that of KH2PO4, respectively. Density functional theory calculations were performed to reveal the origin of the SHG response of compound 3.

Second-Harmonic Generation in Homochiral Antimony Halides Directed by l-Histidine.

Three homochiral organic-inorganic hybrid antimony halides, namely, (L-Hhis)2Sb2Cl8 (1), L-H2his·SbBr5·H2O (2), and (L-H2his)2·Sb3I13·4H2O (3), were prepared to investigate the structure-directing roles of l-histidine (l-his). These compounds feature dimeric, chainlike, and trimeric structures with different optical bandgaps. They display second-harmonic-generation (SHG) responses of 0.1, 2.6, and 0.05 times that of KH2PO4, respectively. Theoretical calculations for compound 2 were carried out to get insights into its structure-property relationship.

Synthesis and structure-dependent optical properties of two new organic-inorganic hybrid antimony(III) chlorides.

Two organic-inorganic hybrid antimony(III) chlorides, namely (C9H26N3)2Sb4Cl18 (1) and (C9H26N3)SbCl6 (2), were prepared using a facile solvent evaporation method. They have low-dimensional structures constructed from SbCl6 octahedra and triply protonated N,N,N',N'',N''-pentamethyldiethylenetriamine cations. The organic cations exhibit different conformations in the two compounds. Compound 1 crystallizes in the centrosymmetric space group P1̄, while compound 2 crystallizes in the noncentrosymmetric space group Pca21. Notably, compound 2 exhibits a moderate second harmonic generation (SHG) response of about 1.3 times that of KH2PO4 (KDP) under 1064 nm laser irradiation. Meanwhile, this compound displays green-yellow luminescence under 342 nm ultraviolet light irradiation, indicating its potential as a bifunctional optical material. Theoretical calculations based on density functional theory were also performed to gain insights into the correlation between their structures and optical properties.