Hydrogen Bond-Assisted Structural Regulation Enables Large Birefringence in Two Antimony Oxalofluoride Crystals.

Two antimony-based oxalofluoride crystals, (NH)Sb(CO)F·HO () and (NH)Sb(CO)F·HO (), were synthesized via a solvent evaporation method. Both compounds feature a [SbOF] pentagonal pyramid and planar π-conjugated [CO] groups, interconnected through hydrogen-bond networks. They exhibit large birefringence values of 0.

Strong second-harmonic generation response in an organic-inorganic hybrid antimony bromide.

A new organic-inorganic hybrid antimony bromide has been prepared using planar nicotinic acid as a structure-directing agent. The compound features a one-dimensional perovskite structure with a strong second-harmonic generation response (SHG) of 3.7 times that of KHPO.

Dual-Sided Multidentate Coordination Strategy Enables Record Birefringence in UV-Transparent Antimony-Based Hybrid Crystals.

Achieving ultrahigh birefringence in UV-transparent materials remains fundamentally constrained by the trade-off between strong optical anisotropy and wide bandgap transparency. Herein, we report a dual-sided multidentate coordination (DMC) strategy to construct two butterfly-shaped UV organic-inorganic hybrid crystals-(CHNO)SbF (PCSF) and (CHNO)SbF (QCSF)-in which planar π-conjugated bidentate ligands symmetrically chelate stereochemically active lone pair (SCALP) Sb centers. This coordination architecture enforces coplanar alignment of optical functional units and promotes dense π-π stacking, thereby significantly enhancing macroscopic birefringence.

Dual Chemical Scissors Strategy Enables 1D Antimony Selenates with Ultraviolet Nonlinear Optical Properties.

The rational, function-driven design of advanced inorganic functional materials remains a significant challenge, primarily attributed to their inherently complex and highly connected 3D frameworks of most oxide-based systems. Herein, we report a "dual chemical scissors" strategy that synergistically combines the effects of fluoride ions and stereochemically active lone pairs to precisely modulate local coordination environments and enable controlled dimensional reduction. Using this approach, we successfully synthesized the first series of non-centrosymmetric 1D antimony selenates-RbSbFSeO (I), RbSbFSeO (II), and RbSbFSeO (III).

Halide Ion-Directed Symmetry Control in π-Conjugated Molecular Crystals.

Two halide-containing π-conjugated molecular crystals, (CHBNO)Cl and (CHBNO)Br, were synthesized using pyridine-4-boronic acid and halide ions of differing ionic radii. (CHBNO)Cl adopts a noncentrosymmetric (NCS) structure and exhibits SHG efficiency comparable to KHPO, along with a wide UV transparency window, making it promising for UV NLO applications. In contrast, (CHBNO)Br crystallizes in a centrosymmetric (CS) structure, exhibiting enhanced birefringence.

Ligand substitution in organic-inorganic hybrid zinc iodides for second-harmonic generation.

Noncentrosymmetric metal halides are promising nonlinear optical (NLO) materials that have prospective applications in optical switching technologies. However, obtaining zinc halides with a large second harmonic generation (SHG) effect is of great challenge due to their ideal tetrahedral configurations. In this study, four organic-inorganic hybrid zinc iodides, namely, (HIm)[ZnI]·HO (1), (HIm)[ZnI(Im)] (2), ZnI(Im) (3), and [ZnI(Im)]I (4) where Im = imidazole, have been synthesized by a ligand substitution approach.

Halogen-Driven Structural Engineering in Tellurium Oxyhalides: Enhanced SHG Response and Broad Optical Transparency.

Oxyhalides are promising candidates for nonlinear optical (NLO) applications due to their unique structural and optical properties. In this study, we report the synthesis of two tellurium-based oxyhalides, TeOCl and TeOCl, which exhibit distinct structural features and exceptional optical performance. TeOCl crystallizes in a noncentrosymmetric 2D layered structure, while TeOCl adopts a centrosymmetric 1D chain arrangement.

Phase-Matching Second-Harmonic Generation in Zero-Dimensional Zinc Thiocyanates Ligated with Chiral Amino Acids.

Two organic-inorganic hybrid solids, namely, Zn(SCN)(L-CHNO) () and Zn(SCN)(L-CHNO)(HO) (), were synthesized by incorporating chiral amino acids into the zinc thiocyanate system. Compound crystallizes as a monomeric complex in the noncentrosymmetric space group 2, while compound features a circular tetrameric structure crystallized in the noncentrosymmetric space group 222. Both compounds exhibit phase-matching second-harmonic generation (SHG) responses, which are 1.

Double Sb-N Coordination Enables Record-High Birefringence in UV-Transparent Crystals.

Achieving high birefringence in ultraviolet (UV)-transparent crystals has remained a significant challenge due to the absence of systematic design methodologies. Herein, we present a novel organic-inorganic coordination strategy that combines π-conjugated organic ligands ([CHN]) with inorganic Sb-based polyhedra featuring stereochemically active lone pairs. This approach facilitates the formation of the first coplanar double Sb-N coordination framework, enabling the synthesis of two new birefringent hybrid crystals: (CHN)SbF(HPO) (PNSP) and (CHN)SbF (PNSF).

Second-Harmonic Generation in Organic-Inorganic Hybrid Cadmium Thiocyanates Containing Terminal Amino Acids.

Using chiral amino acids as terminal ligands, colorless crystals of Cd(SCN)(l-CHNO)(HO)·0.5CHOH () and Cd(SCN)(l-CHNO) () were obtained by a solvent evaporation method. Compound has a layered structure with a moderate second harmonic generation (SHG) efficiency (0.

Enhanced Birefringence and Excellent Thermal Stability in Two Tellurium(IV) Vanadates: KTeOVO and CaTeVO.

Two tellurium(IV) vanadates, KTeOVO and CaTeVO, were synthesized by integrating Te with lone-pair of electrons and V exhibiting the second-order Jahn-Teller effect (SOJT) active centers. Both compounds feature unique one-dimensional chain structures formed by [TeO] and [VO] polyhedra, resulting in notable birefringence values of 0.162 and 0.

In Situ Synthesis of Highly Emissive Manganese Halides with Modified Bisphosphonium Cations toward Information Encryption.

Multisite modulation for organic-inorganic hybrid metal halides (OIMHs) plays an important role in the optimization of their photophysical performance. Herein, we proposed an organic cation modification strategy on the phosphorus sites based on 1,2-Bis(diphenylphosphino)ethane (DPPE) by a simple one-pot solvothermal method. Three zero-dimensional (0D) manganese-based OIMHs, two novel MdppeMnCl·HO and EdppeMnCl, as well as the byproduct [Mn(dppeO)][MnCl] were obtained (Mdppe = methyl-coordinated with DPPE; Edppe = ethyl-coordinated with DPPE; and dppeO is obtained by oxidation of DPPE).

Dual Lone Pair Strategy for High Birefringence in Antimony(III)-Based Tellurite Sulfates with Short-Wave UV Transparency.

We present two novel antimony(III)-based tellurite sulfate crystals, Sb(TeO)(SO)-1̅ (I) and Sb(TeO)(SO)-2/ (II), synthesized using a dual lone pair strategy that incorporates Sb and Te ions into a sulfate framework. This approach significantly enhances the birefringence of these compounds, with values of 0.11 and 0.

Design and Synthesis of Two Sn-Centered Mixed Halide Crystals with Enhanced Birefringence.

Enhancing the optical anisotropy of compounds has attracted significant interest in the optical field. Sn-centered crystals, containing stereochemically active lone pairs, are widely regarded as promising birefringent materials. In this study, we successfully synthesized two novel Sn-centered mixed halide birefringent crystals, NaSnFBr and NaSnFI.

Two l-Proline Cadmium Thiocyanates with Moderate Second-Harmonic-Generation Responses and Large Birefringences.

Two organic-inorganic cadmium thiocyanates, namely, Cd(SCN)(l-CHNO) () and Cd(SCN)(l-CHNO) (), have been synthesized using l-proline as the bridging ligand. The two compounds have double-chain-like and layered structures, respectively. They feature moderate second-harmonic-generation responses (0.

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

Three organic-inorganic metal iodides, namely, (NH)(l-hp)ZnI (), [Cd(l-hp)]CdI (), and (l-Hhp)(l-hp)PbI (), 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 shows a large second-harmonic-generation response of 3.

Optimization of Functional Building Blocks Generates a Substantial Improvement in Birefringence from SnOSO to SnO(OH)(HSO).

In this work, two tin(II)-based sulfates, SnOSO and SnO(OH)(HSO), were synthesized via the mild hydrothermal method. Both compounds employ the Sn cation with stereochemically active lone pair (SCALP) electrons and non-π-conjugated tetrahedral anionic groups SO as the functional structural blocks. Interestingly, the experimental birefringence of SnO(OH)(HSO) is 0.

Amine-directed synthesis, valence state control, and optical properties of two new organic-inorganic tin chlorides.

Two organic-inorganic tin chlorides, namely (CHNCl)SnCl (1) and (CHNCl)SnCl (2), were prepared valence state control using ,,','',''-pentamethyldiethylenetriamine as a structure-directing agent. The two compounds have zero-dimensional structures crystallized in non-centrosymmetric orthorhombic space group 2 and 222, respectively. In compound 1, the divalent tin ion forms a seesaw coordination configuration with four chloride ions, whereas in compound 2, the tetravalent tin ion forms an octahedral coordination configuration with six chloride ions.

Gradual Increase in Birefringence of Antimony Oxalates through Precise Tuning of the Sb/[CO] Ratio.

Birefringent crystals play a crucial role in modulating and controlling the polarization of light in the optical communication and laser industries. Recently, adopting appropriate strategies to enhance the birefringence of crystals has become a prominent area of research focus. Herein, four UV antimony oxalate birefringent crystals, namely, KSb(CO)·3HO, BaSb(CO)·3HO, NaSbO(CO)·6HO, and NaSb(CO)F·2HO, have been successfully synthesized.

Correction: Hydrogen bonding bolstered head-to-tail ligation of functional chromophores in a 0D SbF·glycine adduct for a short-wave ultraviolet nonlinear optical material.

[This corrects the article DOI: 10.1039/D4SC01353K.].

Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction.

This study pioneers a novel strategy for synthesizing solar-blind ultraviolet (UV) nonlinear optical (NLO) crystals through functional groups sequential construction, effectively addressing the inherent trade-offs among broad transmittance, enhanced second-harmonic generation (SHG), and optimal birefringence. We have developed two innovative van der Waals layered germanous phosphites: GeHPO, the first Ge(II)-based oxide NLO crystal which exhibits a black phosphorus-like structure, and K(GeHPO)Br, distinguished by its exceptional birefringence and graphene-like structure. Significantly, GeHPO exhibits a remarkable array of NLO properties, including the highest SHG coefficient recorded among all NLO crystals for phase-matching and generating 266 nm coherent light via quadruple frequency conversion.

SbOSeO and SbO(SeO): Two-Layered Antimony(III) Selenites with Enhanced Birefringence.

Two antimony selenites, SbOSeO and SbO(SeO), were synthesized by simultaneously incorporating stereochemically active lone pair electrons containing SeO and Sb. These compounds are structured with [SbO] polyhedra and [SeO] units within a two-dimensional framework. Both of them exhibit cutoffs at 300 and 330 nm within the ultraviolet (UV) range and demonstrate significant birefringence, with indices of 0.

Two histidine-templated metal phosphate-oxalates: solvent-free synthesis, luminescence, and proton-conducting properties.

Two new histidine-templated metal phosphate-oxalates (MPOs) were prepared under solvent-free conditions. Single-crystal X-ray diffraction analysis reveals that they have layered and chainlike structures, respectively. Under ultraviolet light irradiation, the two MPOs exhibit blue luminescence originating from histidine templates.