Moderate Second Harmonic Generation Research Articles

Achieving Phase-Matching in Nonlinear Optical Materials CsM2In2S6 (M = Cd/In, Hg/In) by the Incorporation of Unprecedented Trigonal Planar MS3 Motifs.

The trigonal planar unit possesses significant hyperpolarizability and polarizability anisotropy, which makes it useful for optimizing nonlinear optical (NLO) materials, however, chalcogenide with this unit has seldom been reported. In this work, a novel approach is introduced by integrating the unprecedented trigonal planar MS3 (M=Cd/In, Hg/In) motifs into the nearly optically isotropic tetrahedral units, resulting in two novel chalcogenides CsM2In2S6 (M=Cd/In, 1; Hg/In, 2). Notably, structures 1 and 2 feature nearly planar triangular units at the center, encircled by three trimers, further interconnecting each other to create 3D frameworks. Importantly, phases 1 and 2 display phase-matching (PM) capabilities, primarily attributed to incorporating trigonal planar MS3 units that additionally enhance polarizability anisotropy. Furthermore, compounds 1 and 2 demonstrate moderate second-harmonic generation (SHG) signals (0.70 and 0.84 × AgGaS2@1.7µm). This study pioneers an efficient strategy for the design of infrared NLO crystals with PM capabilities.

K4Cd3Ge4O13: A Congruent-Melting Germanate Nonlinear Optical Crystal with a Moderate Second-Harmonic Generation Intensity and Broad Transparent Window.

Mid-infrared (IR) nonlinear optical (NLO) materials have generated extensive research interest because of their crucial role in laser technology applications. Here, we report the synthesis of a novel cadmium germanate NLO crystal, K4Cd3Ge4O13, using spontaneous crystallization. K4Cd3Ge4O13 demonstrates a distinct three-dimensional structural framework characterized by twisted [Ge4O13] and [Cd3O10] clusters, composed of [GeO4], [CdO4], [CdO5], and [CdO6] basic building units, respectively, which represents an unprecedented structural feature. The title compound undergoes a desirable congruent melting behavior at about 727 °C. Notably, K4Cd3Ge4O13 demonstrates a short UV cutoff edge at 261 nm, coupled with a wide energy gap of 4.4 eV, and maintains an extended IR transparency window at around 6.0 μm. More importantly, it demonstrates a strong second-harmonic generation activity comparable to that of KH2PO4 (KDP) at 1064 nm. Theoretical analyses further elucidate that the remarkable optical performances of K4Cd3Ge4O13 are predominantly attributed to the cooperative effects of Ge-O and Cd-O bond-based motifs. These desired characteristics underscore the potential of K4Cd3Ge4O13 as a good candidate material for mid-IR NLO applications.

Synthesis, crystal and electronic structures, linear and nonlinear optical properties, and photocurrent response of oxyhalides CeHaVIO4 (Ha = Cl, Br; VI = Mo, W).

Four heteroanionic oxyhalides, CeClMoO4, CeBrMoO4, CeClWO4, and CeBrWO4, have been studied as multifunctional materials, which show a combination of good second harmonic generation (SHG) response and photocurrent signals. Millimeter-sized CeHaVIO4 (Ha = Cl, Br; VI = Mo, W) crystals were grown by halide salt flux. The crystal structure of CeHaVIO4 crystals was accurately determined by single-crystal X-ray diffraction. CeClMoO4, CeBrMoO4, and CeBrWO4 are isostructural to each other, and crystallize in the acentric LaBrMoO4 structure type. CeClWO4 crystallizes in a new structure type with unit cell parameters of a = 19.6059(2) Å, b = 5.89450(10) Å, c = 7.80090(10) Å, and β = 101.4746(8)°. The bandgaps of CeHaVIO4 fall into the range of 2.8(1)-3.1(1) eV, which are much smaller than those of isotypic LaHaVIO4 (Ha = Cl, Br; VI = Mo, W) in the range of 3.9(1)-4.3(1) eV. The narrowing of bandgaps in CeHaVIO4 originates from the presence of partially filled 4f orbitals of cerium atoms, which was confirmed by density functional theory (DFT) calculations. The moderate bandgaps make CeHaVIO4 suitable for infrared nonlinear optical (IR NLO) applications. CeBrMoO4 and CeBrWO4 exhibit moderate SHG responses of 0.58× AGS and 0.46× AGS, respectively, and are both type-I phase-matching materials. Moderate SHG response, easy growth of crystals, high ambient stability, and type-I phase-matching behavior make CeBrMoO4 and CeBrWO4 great materials for IR NLO applications. CeHaVIO4 films also exhibited good photocurrent response upon light radiation. This work demonstrates the rich structural chemistry of the REHaVIO4 (RE = Y, La-Lu; Ha = Cl, Br; VI = Mo, W) family and the potential presence of more multifunctional materials.

Exploring a new short-wavelength nonlinear optical fluoride material featuring unprecedented polar cis-[Zr6F34]10- clusters.

Traditional fluorides are rarely reported as candidates for nonlinear optical (NLO) materials featuring a deep-ultraviolet cutoff edge. Theoretical investigations suggest that the ZrF8 dodecahedron shows large polarizability anisotropy and benefits for large birefringence. Herein, a new fluorine-rich fluoride, K3Ba2Zr6F31, was synthesized by coupling the ZrF8 group, featuring acentric cis-[Zr6F34]10- clusters with a 63-screw axis. Significantly, K3Ba2Zr6F31 exhibits a short UV cutoff edge (below 200 nm) and moderate second-harmonic generation (SHG) response (0.5 × KH2PO4). It also possesses a relatively large birefringence (0.08@1064 nm), together with a broad transparency window (2.5-21.1 μm). First-principles calculations suggest that the cis-[Zr6F34]10- cluster built by ZrF8 dodecahedra are the dominant contributors to the large band gap (7.89 eV, cal.) and SHG response simultaneously. Such systematic work highlights that Zr-based fluorides afford a new paradigm for the development of efficient NLO materials with a short UV cutoff edge.

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

Two organic-inorganic tin chlorides, namely (C9H26N3Cl)SnCl4 (1) and (C9H26N3Cl)SnCl6 (2), were prepared via valence state control using N,N,N',N'',N''-pentamethyldiethylenetriamine as a structure-directing agent. The two compounds have zero-dimensional structures crystallized in non-centrosymmetric orthorhombic space group Cmc21 and P212121, 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. The two compounds show a moderate second-harmonic generation response under 1064 nm laser irradiation. Notably, compound 2 displays a bright orange luminescence with a photoluminescence quantum yield of 19.67%. Theoretical calculations were performed to gain insights into the optical properties of the two compounds.

K(NH4)Zn2(PO4)2: a Beryllium-Free Sr2Be2B2O7 Derivative with Enhanced Interlayer Connectivity.

A novel zinc phosphate derivative of Sr2Be2B2O7 (SBBO), K(NH4)Zn2(PO4)2 (KNZP), featuring [Zn2P2O8]∞2- double layers akin to the [Be2B2O7]∞4- layers in SBBO, was successfully synthesized via a moderate hydrothermal method. Through the substitution of BeO4 and BO3 with ZnO4 and PO4, the issue of toxicity has been effectively resolved, while the enhanced interlayer interactions facilitated by covalent and hydrogen bonding in KNZP overcome the inherent structural instability. Notably, KNZP exhibits a wide transparent window and a moderate second-harmonic generation (SHG) intensity, reaching 0.7 times that of KH2PO4 (KDP), rendering it type-I phase-matchable, indicating that it is a promising UV nonlinear optical (NLO) material.

Excellent Nonlinear Optical M[M4 Cl][Ga11 S20 ] (M = A/Ba, A = K, Rb) Achieved by Unusual Cationic Substitution Strategy.

The typical chalcopyrite AgGaQ2 (Q = S, Se) are commercial infrared (IR) second-order nonlinear optical (NLO) materials; however, they suffer from unexpected laser-induced damage thresholds (LIDTs) primairy due to their narrow band gaps. Herein, what sets this apart from previously reported chemical substitutions is the utilization of an unusual cationic substitution strategy, represented by [[SZn4 ]S12 + [S4 Zn13 ]S24 + 11ZnS4 ⇒ MS12 + [M4 Cl]S24 + 11GaS4 ], in which the covalent Sx Zny units in the diamond-like sphalerite ZnS are synergistically replaced by cationic Mx Cly units, resulting in two novel salt-inclusion sulfides, M[M4 Cl][Ga11 S20 ] (M = A/Ba, A = K, 1; Rb, 2). As expected, the introduction of mixed cations in the GaS4 anionic frameworks of 1 and 2 leads to wide band gaps (3.04 and 3.01 eV), which exceeds the value of AgGaS2 , facilitating the improvement of high LIDTs (9.4 and 10.3 × AgGaS2 @1.06 µm, respectively). Furthermore, compounds 1 and 2 exhibit moderate second-harmonic generation intensities (0.84 and 0.78 × AgGaS2 @2.9 µm, respectively), mainly originating from the orderly packing tetrahedral GaS4 units. Importantly, this study demonstrates the successful application of the cationic substitution strategy based on diamond-like structures to provide a feasible chemical design insight for constructing high-performance NLO materials.

Four UV Transparent Linear and Nonlinear Optical Materials Explored from Pure Selenite Compounds

AbstractUV nonlinear optical materials require the simultaneous achievement of a large second harmonic generation (SHG) coefficient (≥1 × KH2PO4 (KDP), dij > 0.39 pmV−1), wide bandgap (λ < 300 nm, Eg > 4.2 eV), and moderate birefringence (0.05‐0.10@1064 nm) in a single structure. Therefore, designing UV nonlinear optical materials with excellent comprehensive performance is a challenging task. Herein, four UV transparent selenite materials are successfully obtained, namely, Al2(SeO3)3(H2O)3 (1), Ga2(SeO3)3(H2O)3 (2), NaGa3(HSeO3)6(SeO3)2 (3), and Cd5Ga4(HSeO3)2(SeO3)10 (4), through rational design and screening in the pure selenite system. Al2(SeO3)3(H2O)3 (1) and Ga2(SeO3)3(H2O)3 (2) are UV nonlinear optical materials with balanced properties, exhibiting moderate SHG responses (1.2 and 1.1 × KDP), appropriate birefringence (0.084 and 0.076@1064 nm), and wide bandgaps (5.5 and 5.3 eV). Such bandgaps are the largest in the reported pure selenite nonlinear optical (NLO) materials. This work further demonstrates that pure selenite is a good candidate for UV NLO materials.

Wide band gaps in nonlinear optical materials AMgAgGa6S11 (A = K, Rb) achieved by the incorporation of dual s-block elements in Ag-based sulfide

Infrared (IR) nonlinear optical (NLO) material with a concurrently wide band gap and significant NLO coefficient in a single crystal is an incompatible but addressable challenge. Hence, for the first time, the AgGaS2 structure evolved into an Ag-based sulfide system integrating dual s-block elements, guiding the discovery of two NLO crystals named AMgAgGa6S11 (A = K, 1; Rb, 2). Structurally, title phases possess a novel NLO functional motif [AgGa6S17] assembled by two C2-type supertetrahedra through a shared [AgS4] tetrahedron, in which the electropositive cations A+ and Mg2+ are embedded. Thus, compounds 1 and 2 display emulative band gaps (3.15 and 3.25 eV, exceeding that of 2.65 eV in AgGaS2) toward optimizing the laser-induced damage thresholds (3.1 and 3.2 × AgGaS2 @1064 nm). Remarkably, the noncentrosymmetric phases 1 and 2 exhibit moderate second-harmonic generation (SHG) responses (0.6 and 0.7 × AgGaS2 @1910 nm), the greater-than-commercial half of the AgGaS2. To the best of our current knowledge, an experimental birefringence of 1 and 2 (0.029 and 0.027, @546 nm) is first observed in quinary ordered chalcogenides, indicating that samples 1 and 2 meet phase-matching conditions at the incident laser of 1910 nm. All these observations demonstrate that crystals 1 and 2 can become prospective NLO materials. This research will pave the way for discovering excellent IR NLO crystals with wide band gaps and impressive NLO coefficients by incorporating multiple strong electropositive elements into chalcogenides.

Centrosymmetric Rb2Sb(C2O4)2.5(H2O)3 and Noncentrosymmetric RbSb2(C2O4)F5: Two Antimony (III) Oxalates as UV Optical Materials.

Herein, we have successfully synthesized two rubidium antimony (III) oxalates, namely, Rb2Sb(C2O4)2.5(H2O)3 and RbSb2(C2O4)F5, utilizing a low-temperature hydrothermal method. These two compounds share a similar chemical composition, consisting of Sb3+ cations with active lone pair electrons, alkali metal Rb+ ions, and planar π-conjugated C2O42- anions. However, they exhibit different symmetries, Rb2Sb(C2O4)2.5(H2O)3 is centrosymmetric (CS), while RbSb2(C2O4)F5 is noncentrosymmetric (NCS), which should be caused by the presence of F- ions. Notably, the NCS compound, RbSb2(C2O4)F5, demonstrates a moderate second-harmonic generation (SHG) response, approximately 1.3 times that of KH2PO4 (KDP), and exhibits a large birefringence of 0.09 at 546 nm. These characteristics indicate that RbSb2(C2O4)F5 holds promising potential as a nonlinear optical material for ultraviolet (UV) applications. Detailed structural analysis and theoretical calculations confirm that the excellent optical properties arise from the synergistic effects between Sb3+ cations with SCALP and planar π-conjugated [C2O4]2- groups.

Hg3(SeO3)2(SO4): A UV Nonlinear Optical Mercury Selenite Sulfate Constructed by Neat [Hg6O8(SeO3)4]∞ Layers and SO4 Tetrahedra.

A novel mercury selenite sulfate named Hg3(SeO3)2(SO4) has been successfully synthesized under a mild hydrothermal method. Hg3(SeO3)2(SO4) crystallizes in a monoclinic space group P21 and features a unique three-dimensional (3D) frame structure formed by [Hg6O8(SeO3)4]∞ layers and SO4 tetrahedra, which enables it to exhibit a comprehensive performance of a moderate second-harmonic generation (SHG) response of approximately 1.3 times that of baseline KH2PO4 (KDP), a moderate birefringence (0.118@546 nm), and a wide band gap (4.70 eV), which indicates that it has potential for application as an ultraviolet (UV) nonlinear optical material. Detailed theoretical calculations show that the Hg2+-based polyhedra with large polarizability and deformability and the SeO3 groups with stereochemically active lone pair (SCALP) electrons are the main contributors to moderate optical properties.

Solvent-free synthesis of magnesium phosphite-oxalates that show second-harmonic generation responses.

Two new magnesium phosphite-oxalates were prepared under solvent-free conditions using different amines as structure-directing agents. They feature noncentrosymmetric structures with sql and dia topologies, respectively. The two compounds show moderate second-harmonic generation (SHG) responses under 1064 nm laser irradiation. Theoretical calculations were performed to reveal the origin of their SHG responses.

Phosphites: A Nonlinear Optical Materials System with a Wide Band Gap and Moderate Second-Harmonic Generation Effect

Ultraviolet (UV) nonlinear optical (NLO) materials have crucial practical applications in modern laser science and technology. Phosphates are promising candidates for searching UV NLO materials. However, small optical anisotropy of high-symmetrized (PO4)3- tetrahedron hinders phase matching (PM) in the UV wavelength range. Herein, a low-symmetrized phosphite anionic group (HPO3)2- is proposed as a new NLO-active group that exhibits a larger optical anisotropy and second-harmonic generation (SHG) coefficients than (PO4)3-. Accordingly, two phosphites, (C(NH2)3)2Zn(HPO3)2 and [Al2(HPO3)3(H2O)3]·H2O, that contain (HPO3)2- groups are screened out and synthesized. The UV absorption edges of the two compounds are 6.18 and 6.23 eV, respectively. (C(NH2)3)2Zn(HPO3)2 exhibited an SHG intensity of 1 times that of KDP at 1064 nm. This work proposes a new NLO-active fundamental building unit (FBU) and a new materials system for searching NLO materials.

(C4H10NO)PbX3 (X = Cl, Br): Design of Two Lead Halide Perovskite Crystals with Moderate Nonlinear Optical Properties.

Introducing electronegative species into organic constituents was considered to be one effective strategy for adjusting crystal symmetry and designing new nonlinear optical (NLO) materials. By substitution of C4 in piperidine (C5H11N) with electronegative oxygen, organic morpholine (C4H9NO) was easily obtained. Therefore, to design NLO crystals, we focused on combinations of stereochemically active lone-pair (SCALP) cation (Pb2+)-based chloride and bromide with morpholine molecules. In this work, two lead halide hybrid perovskite (C4H10NO)PbX3 (X = Cl, Br, abbreviated as MPbCl3 and MPbBr3, respectively) single crystals with moderate nonlinear optical properties were synthesized by a slow evaporation method. The two title crystals belong to orthorhombic space group P212121 with one-dimensional (1D) chainlike perovskite structures. Theoretical calculations revealed that the second harmonic generation (SHG) responses mainly originate from distorted {PbX6} octahedrons of the inorganic framework. Remarkably, moderate phase-matching SHG effects of about 0.70 and 0.81 times KH2PO4, large birefringences of 0.098 and 0.111 at 1064 nm, and large laser damage thresholds (LDTs) of 19.94 and 46.82 MW/cm2 were estimated for MPbCl3 and MPbBr3, respectively. This work provides a novel strategy for new purpose-designed hybrid NLO crystals by adjustment and modulation of chemical modification.

Pb5(GeO4)(Ge2O7) and Pb3.32Ca1.68(GeO4)(Ge2O7): Two Nonlinear Optical Germanates Induced by Diverse PbOx Polyhedra.

Oxide nonlinear optical (NLO) crystals have drawn wide interest for their comprehensive physical performances including wide infrared (IR) transparency ranges, large band gaps, and good stability in open air. Here, two isostructural germanate oxides, Pb5(GeO4)(Ge2O7) (1) and Pb3.32Ca1.68(GeO4)(Ge2O7) (2), adopting the noncentrosymmetric (NCS) space group P6̅, were composed via a conventional solid-state reaction. The latter was designed by the partial cation substitution strategy based on parent 1. The whole structures of 1 and 2 are composed of isolated distorted GeO4 tetrahedra, Ge2O7 dimers, and diverse M (M = Pb, Ca, or Pb/Ca)-centered polyhedra. They exhibit second-harmonic generation (SHG) responses around 3.3 and 1.4 times that of KH2PO4 (KDP) under 1.064 μm laser radiation, respectively. Theoretical calculation results reveal that the Pb2+ cations with stereo-active long pair (SCALP) electrons of 1 favor the large SHG response, while Pb-based polyhedra showing inert SCALP electrons make predominant contributions to the moderate SHG effect of 2.

Modulating Two Pairs of Chiral DyIII Enantiomers by Distinct β-Diketone Ligands to Show Giant Differences in Single-Ion Magnet Performance and Nonlinear Optical Response.

Using Dy(dbm)3(H2O) and Dy(btfa)3(H2O)2 to react with enantiopure N-donors, (-)/(+)-4,5-pinenepyridyl-2-pyrazine (LR/LS), respectively, two pairs of chiral DyIII enantiomers, Dy(dbm)3LR/Dy(dbm)3LS (R-1-Dy/S-1-Dy) and Dy(btfa)3LR/Dy(btfa)3LS (R-2-Dy/S-2-Dy) were obtained, wherein one of the benzene rings of dbm- (dibenzoylmethanate) in R-1-Dy/S-1-Dy is displaced by the -CF3 group of btfa- (4,4,4-trifluoro-1-phenyl-1,3-butanedionate) in R-2-Dy/S-2-Dy. Interestingly, this substitution results not only in giant differences in their single-ion magnetic (SIM) performances but also in their completely different nonlinear optical (NLO) responses. R-1-Dy presents a large effective energy barrier (Ueff = 265.47 K) under zero applied field, being more than 4 × R-2-Dy (61.40 K). The discrepancy on their magnetic performances has been further elucidated by ab initio calculations. Meanwhile, R-1-Dy/S-1-Dy display the strongest third-harmonic generation responses (35/33 × α-SiO2) among the known lanthanide NLO-active coordination compounds (CCs). On the contrary, R-2-Dy/S-2-Dy exhibit moderate second-harmonic generation responses (0.65/0.70 × KDP). These results not only give the first example of the CCs with both SMM/SIM behavior and a THG response but also provide an efficient strategy for achieving the function regulation and switch in multifunctional CCs.

Design of a diamond-like infrared nonlinear optical material LiBS2 with ultra-wide band gap

The exploration of new infrared (IR) nonlinear optical (NLO) materials with large second-harmonic generation (SHG) responses and wide band gap (Eg) is an urgent need but challenging. Starting from the superior unit combination strategy and considering the advantages of borates, chalcogenides and Li elements, we have focused our attention on the exploration of IR NLO materials in the Li-based thioborates. Four novel non-centrosymmetric LiBS2 structures, were obtained successfully through crystal structure prediction by analogy and structural optimization based on the thermodynamic and dynamic stability analysis. Among them, LiBS2-I exhibits an ultra-wide band gap Eg = 4.4 eV, moderate SHG response 0.6 × AgGaS2, and suitable birefringence Δn = 0.04 at 1064 nm, which satisfies the good balance between Eg ≥ 3.0 eV and dij ≥ 0.5 × AgGaS2. The role of microscopic units [BS4] in NLO effect was investigated. This work enriches the structural diversity of thioborates and provides a new approach to the exploration of excellent IR NLO materials.

Rational design of a promising oxychalcogenide infrared nonlinear optical crystal.

Oxychalcogenides with the performance-advantages of both chalcogenides and oxides are emerging materials class for infrared (IR) nonlinear optical (NLO) crystals that can expand the wavelength of solid-state lasers to IR regions and are of importance in industrial and civil applications. But rationally designing a high-performance oxychalcogenide NLO crystal remains a great challenge. Herein, we chose the melilite-type Sr2ZnSi2O7 as the structure template. Through part isovalent substitution of S2− for O2− anions, the first hetero-anionic thiostannate Sr2ZnSn2OS6 with wide IR transmission has been synthesized. More importantly, compared to the maternal oxide, Sr2ZnSi2O7, the second harmonic generation (SHG) response of Sr2ZnSn2OS6 is enhanced by two orders of magnitude. In addition, Sr2ZnSn2OS6 can exhibit a large band-gap and high laser damage threshold. These advantages make Sr2ZnSn2OS6 a promising IR NLO crystal. Our research will provide insights into the rational design of new IR NLO crystals.

AAg3Ga8Se14 (A = Rb, Cs): second-harmonic generation responses realized through the parallel arrangement of AgSe4 and GaSe4 tetrahedrons.

Two new quaternary selenides AAg3Ga8Se14, (A = Rb, 1; Cs, 2) were synthesised via solid-state reaction in sealed silica tubes. Compounds 1 and 2 crystallised in the monoclinic space group Cm (no. 8) and their three-dimensional [Ag3Ga8Se14]- anionic frameworks were comprised of AgSe4 and GaSe4 tetrahedrons. Their UV-Vis-near infrared diffuse reflectance spectra showed that 1 and 2 possessed wide band gaps of 2.17 and 2.10 eV, respectively. Notably, under incident laser irradiation at 1910 nm, compounds 1 and 2 presented moderate second-harmonic generation responses of 0.6 and 0.7 × AgGaS2, respectively, with phase-matching behaviours due to the parallel arrangement of nonlinear optical (NLO) functional tetrahedral AgSe4 and GaSe4 units. The laser-induced damage thresholds of 1 and 2 were estimated to be 25.4 and 18.0 MW cm-2, respectively, which were 2.1 and 1.5 times the threshold of AgGaS2. This study revealed that the title selenides, which were constructed from tetrahedral units arranged in a parallel array, are promising infrared NLO materials.

Noncentrosymmetric (KBa0.5)In2Se4 and (K0.58Ba0.71)(Ga0.89In1.11)Se4 derived from centrosymmetric BaIn2Se4 via partial cation substitution: structural chemistry and nonlinear optical activity

Two new noncentrosymmetric multinary selenides, (KBa0.5)In2Se4 (1) and (K0.58Ba0.71)(Ga0.89In1.11)Se4 (2), have been synthesized using a high-temperature flux method at 1123 K. They crystallize in the tetragonal noncentrosymmetric space group I4cm with cell parameters: a = 8.0277(2), c = 6.7654(3) Å, V = 435.99(3) Å3 for 1; a = 8.0296(4), c = 6.5403(9) Å, V = 421.68(7) Å3 for 2 vs the orthorhombic centrosymmetric space group Fddd for BaIn2Se4. Their one-dimensional structures are constructed by [(MSe2)–]n (M = Ga, In) chains composed of MSe4 tetrahedra via sharing edges, and K+/Ba2+ cation occupying the interchain cavities. They both show moderate second-harmonic generation responses about 0.5 × AgGaS2@2.1 μm. UV-vis-NIR diffuse reflectance spectroscopy measurement shows that the optical band gaps of 1 and 2 are about 2.60 and 2.34 eV, respectively. Theoretical calculations are also carried out to analyze their electronic structures and optical properties.