Hybrid Metal‐Halide Infrared Nonlinear Optical Crystals of (TMEDA)MI₅ (M = Sb, Bi) with High Stability

Abstract

Organic–inorganic metal halides (OIMHs) with unique structural flexibility possess excellent photoelectric properties. They are regarded as next‐generation photovoltaic materials, phosphors, semiconductors, and ferroelectrics. The metal‐halide units in OIMHs are good microscopic building blocks of nonlinear optical crystals for laser wavelength conversion. However, most OIMHs are absent from nonlinear optics owing to their macroscopic nonlinear optical (NLO)‐inactive centrosymmetric crystal structure. In this study, two new lead‐free OIMHs, (TMEDA)SbI5 and (TMEDA)BiI5 (where TMEDA2+ is N,N,N′‐trimethylethylenediammonium), having 1D structure, crystallized in the orthorhombic system with a non‐centrosymmetric P212121 space group, are synthesized. Remarkably, upon 2090 nm laser irradiation, both compounds possess a strong infrared (IR) nonlinear optical response of the same magnitude as AgGaS2, which is a benchmark semiconductor‐type nonlinear optical crystal. In addition, under the excitation of ultraviolet and visible lights, both compounds produce self‐trapped exciton‐induced red‐light emission. First‐principles electronic structure calculations reveal that the optical properties originate from the electronic transitions within the inorganic metal‐halide group. The obtained results indicate that both compounds are potential photoelectric materials for laser frequency conversion and fluorescence, and the observation of NLO effect in these two compounds verifies that OIMHs are also good candidates for NLO crystals.

Symmetry breaking of A3M2X9-type perovskite derivatives induced by polar quaternary ammonium cations: achieving efficient nonlinear optical properties

“…The distortion degree is calculated as (Δd ¼ 1=6 P 6 i¼1 ½ðd i À d 0 Þ=d 0 2 . d i is the Bi-Cl bond length and d 0 is the mean Bi-Cl bond length) 45 of two [BiCl 6 ] 3− octahedra which are 3.6 × 10 −3 and 4.3 × 10 −3 , respectively, and are much higher than those of (TMEDA)BiI 5 (0.957 × 10 −3 ), 46 (TMEDA)SbI 5 (1.489 × 10 −3 ), 46 (PBA) 4 BiBr 7 •H 2 O (3.27 × 10 −3 ), 47 (PBA) 4 BiI 7 •H 2 O (3.20 × 10 −3 ), 47 (PBA) 4 InBr 7 •H 2 O (2.61 × 10 −3 ), 47 (R-/S-MBA)BiI 4 (1.5 × 10 −3 and 2.3 × 10 −3 ), 48 and (R-/S-MPEA) 2 CuCl 4 (3.32 × 10 −4 and 3.07 × 10 −4 ), 49 indicating that the lone pair of Bi 3+ cations in (BTA) 3 BiCl 9 is more chemically active. In addition, organic moieties arranged in order connect to the inorganic [Bi 2 X 9 ] 3− polyhedra via weak C-H⋯Cl hydrogen bonding (see Fig.…”

Nearly one-fold enhancement in photoluminescence quantum yield for isostructural zero-dimensional hybrid antimony(iii) bromides by supramolecular interaction adjustments

“…According to previous studies, STEs correlate well with the distortion level of an inorganic polyhedron in 0D OIMHs. 9,16,19,22,26,37,38,[57][58][59][60][61] Herein, the relationship between structures and PL performances is discussed by calculating the distortions of inorganic [SbBr 5 ] 2− anions. The distortions based on Sb-Br bond lengths and Br-Sb-Br angle variances are defined as follows.…”

Nonlinear Optical Benzoindolium-Based Single Crystals: H-Contacts Induced Noncentrosymmetric Alignment Approaching Efficient Terahertz-Wave Generation

“…3-Hydroxybenzaldehyde was used and then the same synthesis procedure was followed. 1 H NMR (400 MHz, DMSO) δ 9.89 (s, 1H), 8.41 (t, J = 11.9 Hz, 2H), 8.30 (d, J = 8.9 Hz, 1H), 8.22 (d, J = 8.0 Hz, 1H), 8.12 (d, J = 9.0 Hz, 1H), 7.81 (dd, J = 11.3, 4.1 Hz, 1H), 7.73 (t, J = 7.2 Hz, 1H), 7.66 (dd, J = 12.3, 4.2 Hz, 2H), 7.58 (s, 1H), 7.40 (t, J = 7.9 Hz, 1H), 7.05 (dd, J = 8.0, 2.0 Hz, 1H), 4.28 (s, 3H), 2.00 (s, 6H).…”

“…4-Hydroxybenzaldehyde was used and then the same synthesis procedure was followed. 1 Single-Crystal X-ray Diffraction. Selected single crystals were mounted on a glass fiber separately.…”