Second-order Jahn-Teller Research Articles

Layered ferrielectric crystals CuInP2S(Se)6: a study from the first principles

ABSTRACTLayered CuInPS(Se) crystals in ferrielectric and paraelectric phases were investigated for the first time via the plane-wave pseudo-potential methodology within density functional theory (DFT). Was proved that structural and electronic properties of the van der Waals layered crystals should be calculated applying dispersion correction to the DFT formalism. The partial and projected density of states were used to evaluate the electronic band structure changes under phase transition. Instability of the CuInPS(Se) crystals was successfully explained by the second-order Jahn-Teller effect.

Bi2Te2O6(NO3)2(OH)2(H2O): A layered bismuth tellurium nitrate hydroxide with multiple noncentrosymmetric chromophores

Crystals of a novel bismuth tellurium nitrate hydroxide, Bi2Te2O6(NO3)2(OH)2(H2O), with noncentrosymmetric (NCS) structure have been grown in high yield through a hydrothermal reaction using TeO2, Bi(NO3)3·5H2O, and HNO3 as reagents. Bi2Te2O6(NO3)2(OH)2(H2O) exhibits a layered structure consisting of polyhedra with second-order Jahn-Teller (SOJT) distortive cations, i.e., BiO5, BiO7, Te4+O3, and Te6+O6, as well as anionic π-delocalized NO3− groups. Infrared spectral data not only show all of the vibrations for the constituting bonds, but confirm the existence of -OH groups in the framework of the title compound. UV–vis diffuse reflectance spectrum indicates that Bi2Te2O6(NO3)2(OH)2(H2O) reveals a band gap of ca. 4.0 eV. Thermogravimetric analysis along with powder X-ray diffraction measurements at different temperatures suggest that the crystallinity of Bi2Te2O6(NO3)2(OH)2(H2O) is maintained up to ca. 400 °C. Powder second-harmonic generation (SHG) measurements using 1064 nm radiation reveal that Bi2Te2O6(NO3)2(OH)2(H2O) has SHG efficiency of ca. 20 times that of α-SiO2 and is phase-matchable (Type-I). Local dipole moment calculations for the polyhedra of SOJT distortive cations in Bi2Te2O6(NO3)2(OH)2(H2O) are also presented.

High-Pressure Synthesis, Crystal Structure, Chemical Bonding, and Ferroelectricity of LiNbO3-Type LiSbO3.

A polar LiNbO3 (LN)-type oxide LiSbO3 was synthesized by a high-temperature heat treatment under a pressure of 7.7 GPa and found to exhibit ferroelectricity. The crystal structural refinement using the data of synchrotron powder X-ray diffraction and neutron diffraction and the electronic structure calculation of LN-type LiSbO3 suggest a covalent-bonding character between Sb and O. When comparing the distortion of BO6 in LN-type ABO3, the distortions of SbO6 in LiSbO3 and SnO6 in ZnSnO3, which included a B cation with a d10 electronic configuration, were smaller than those of BO6 in LN-type oxides having the second-order Jahn-Teller active B cation, e.g., LiNbO3 and ZnTiO3. The temperature dependence of the lattice parameters, second harmonic generation, dielectric permittivity, and differential scanning calorimetry made it clear that a second-order ferroelectric-paraelectric phase transition occurs at a Curie temperature of Tc = 605 ± 10 K in LN-type LiSbO3. Further, first-principles density functional theory calculation suggested that perovskite-type LiSbO3 is less stable than LN-type LiSbO3 under even high pressure, and the ambient phase of LiSbO3 directly transforms to LN-type LiSbO3 under high pressure. The phase stability of LN-type LiSbO3 and the polar and ferroelectric properties are rationalized by the covalent bonding of Sb-O and the relatively weak Coulomb repulsion between Li+ and Sb5+.

Hybrid Improper Ferroelectricity in (Sr,Ca)3Sn2O7 and Beyond: Universal Relationship between Ferroelectric Transition Temperature and Tolerance Factor in n = 2 Ruddlesden-Popper Phases.

Hybrid improper ferroelectricity, which utilizes nonpolar but ubiquitous rotational/tilting distortions to create polarization, offers an attractive route to the discovery of new ferroelectric and multiferroic materials because its activity derives from geometric rather than electronic origins. Design approachesblending group theory and first principles can be utilized to explore the crystal symmetries of ferroelectric ground states, but in general, they do not make accurate predictions for some important parameters of ferroelectrics, such as Curie temperature ( TC). Here, we establish a predictive and quantitative relationship between TC and the Goldschmidt tolerance factor, t, by employing n = 2 Ruddlesden-Popper (RP) A3B2O7 as a prototypical example of hybrid improper ferroelectrics. The focus is placed on an RP system, (Sr1- xCa x)3Sn2O7 ( x = 0, 0.1, and 0.2), which allows for the investigation of the purely geometric (ionic size) effect on ferroelectric transitions, due to the absence of the second-order Jahn-Teller active (d0 and 6s2) cations that often lead to ferroelectric distortions through electronic mechanisms. We observe a ferroelectric-to-paraelectric transition with TC = 410 K for Sr3Sn2O7. We also find that the TC increases linearly up to 800 K upon increasing the Ca2+ content, i.e., upon decreasing the value of t. Remarkably, this linear relationship is applicable to the suite of all known A3B2O7hybrid improperferroelectrics, indicating that the TC correlates with the simple crystal chemistry descriptor, t, based on the ionic size mismatch. This study provides a predictive guideline for estimating the TC of a given material, which would complement the convergentgroup-theoretical and first-principles design approach.

Excellent Infrared Nonlinear Optical Crystals BaMO(IO₃)₅ (M = V, Ta) Predicted by First Principle Calculations.

Two nonlinear optical crystals, BaVO(IO3)5 and BaTaO(IO3)5, are designed by substituting Nb with V and Ta, respectively, in BaNbO(IO3)5, which is itself a recently synthesized infrared nonlinear optical (NLO) material. The designs of BaVO(IO3)5 and BaTaO(IO3)5 from BaNbO(IO3)5 are based on the following motivation: BaVO(IO3)5 should have a larger second-harmonic generation (SHG) coefficient than BaNbO(IO3)5, as V will result in a stronger second-order Jahn-Teller effect than Nb due to its smaller ion radius; at the same time, BaTaO(IO3)5 should have a larger laser-damage threshold, due to the fact that Ta has a smaller electronegativity leading to a greater band-gap. Established on reliable first-principle calculations, it is demonstrated that BaVO(IO3)5 has a much larger SHG coefficient than BaNbO(IO3)5 (23.42 × 10−9 vs. 18.66 × 10−9 esu); and BaTaO(IO3)5 has a significantly greater band-gap than BaNbO(IO3)5 (4.20 vs. 3.55 eV). Meanwhile, the absorption spectra and birefringences of both BaVO(IO3)5 and BaTaO(IO3)5 are acceptable for practice, suggesting that these two crystals can both be expected to be excellent infrared NLO materials.

Second-Order Jahn–Teller (SOJT) Structural Distortions in Multiply Bonded Higher Main Group Compounds

The geometrical deviations from planar to folded or from linear to bent structures observed in multiply bonded heavy main group element analogues of ethylene and acetylene are treated from a second-order Jahn–Teller (SOJT) perspective. The structural distortions can be regarded as a consequence of a mixing of the filled highest occupied molecular orbital (HOMO) and an unoccupied orbital (LUMO+1). This mixing stabilizes the HOMO and destabilizes the unoccupied LUMO+1 orbital and produces nonbonding electron density, which causes the geometrical distortion through interelectronic repulsion. This occurs more readily in the heavier species because of their generally weaker bonds, which permit a closer approach and hence greater interaction of the molecular levels. Predicting which geometrical distortion enables the HOMO/LUMO+1 mixing requires knowledge of the symmetries of these frontier orbitals and the symmetry of the distortion. For the undistorted structures the product of the symmetries of the interactin...

Mo6+ Cation Enrichment of the Structure Chemistry of Iodates: Syntheses, Structures, and Calculations of Ba(MoO2)2(IO3)4O, Ba3[(MoO2)2(IO3)4O(OH)4]·2H2O, and Sr[(MoO2)6(IO4)2O4]·H2O

The three metal iodates Ba(MoO2)2(IO3)4O (1), Ba3[(MoO2)2(IO3)4O(OH)4]·2H2O (2), and Sr[(MoO2)6(IO4)2O4]·H2O (3) have been successfully synthesized by introducing second-order Jahn-Teller distorted Mo6+ cations by a mild hydrothermal method. Single-crystal X-ray diffraction (XRD) was used to determine the structures of the three title compounds. In compound 1, the [Mo2O11]10- dimers connect with the [IO3]- units by sharing oxygen atoms to form two-dimensional (2D) layers that are separated by the Ba2+ cations. For comparison, the [Mo2O11]10- dimers and the [IO3]- units are isolated in compound 2, and they are connected by the [BaO11]20- polyhedra forming a 3D network. For compound 3, the [MoO6]6- polyhedra link with each other by corner and edge sharing to build 2D corrugated layers with tunnels containing isolated [IO4]3- units. The [SrO9]16- polyhedra link the 2D corrugated layers to form a 3D network. The infrared (IR) spectra, the ultraviolet-visible-near-infrared (UV-vis-NIR) diffuse reflectance spectra, and thermal stabilities of compounds 1 and 2 are presented. In addition, the theoretical calculations are also carried out to evaluate their band gaps and density of states.

Rb3 VO(O2 )2 CO3 : A Four-in-One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second-Harmonic Generation Response.

A nonlinear optical (NLO) carbonatoperoxovanadate, Rb3 VO(O2 )2 CO3 , was synthesized through a simple solution-evaporation method in phase-pure form. Single-crystal X-ray diffraction revealed that the structure of Rb3 VO(O2 )2 CO3 consists of important noncentrosymmetric (NCS) chromophores, that is, π-delocalized (CO3 )2- groups, a second-order Jahn-Teller (SOJT) distortive V5+ cation, and π-localized distorted O22- groups, as well as charge-balancing polarizable Rb+ ions. The powder second-harmonic generation (SHG) measurements indicated that Rb3 VO(O2 )2 CO3 is phase-matchable (Type I) and exhibits a remarkably strong SHG response circa 21.0 times that of potassium dihydrogen phosphate (KDP), which is the largest efficiency observed among carbonate NLO materials. First-principles calculation analysis suggests that the extremely large SHG response of Rb3 VO(O2 )2 CO3 is attributed to the synergistic effect of the cooperation of all the constituting NCS chromophores.

Rb3VO(O2)2CO3: A Four‐in‐One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second‐Harmonic Generation Response

AbstractA nonlinear optical (NLO) carbonatoperoxovanadate, Rb3VO(O2)2CO3, was synthesized through a simple solution‐evaporation method in phase‐pure form. Single‐crystal X‐ray diffraction revealed that the structure of Rb3VO(O2)2CO3 consists of important noncentrosymmetric (NCS) chromophores, that is, π‐delocalized (CO3)2− groups, a second‐order Jahn–Teller (SOJT) distortive V5+ cation, and π‐localized distorted O22− groups, as well as charge‐balancing polarizable Rb+ ions. The powder second‐harmonic generation (SHG) measurements indicated that Rb3VO(O2)2CO3 is phase‐matchable (Type I) and exhibits a remarkably strong SHG response circa 21.0 times that of potassium dihydrogen phosphate (KDP), which is the largest efficiency observed among carbonate NLO materials. First‐principles calculation analysis suggests that the extremely large SHG response of Rb3VO(O2)2CO3 is attributed to the synergistic effect of the cooperation of all the constituting NCS chromophores.

Unusual Ferroelectricity in Two-Dimensional Perovskite Oxide Thin Films.

Two-dimensional (2D) ferroelectricity have attracted much attention due to their applications in novel miniaturized devices such as nonvolatile memories, field effect transistors, and sensors. Since most of the commercial ferroelectric (FE) devices are based on ABO3 perovskite oxides, it is important to investigate the properties of 2D ferroelectricity in perovskite oxide thin films. Here, based on density functional theory (DFT) calculations, we find that there exist three kinds of in-plane FE states that originate from different microscopic mechanisms: (i) a proper FE state with the polarization along [110] due to the second-order Jahn-Teller effect related to the B ion with empty d-orbitals; (ii) a robust FE state with the polarization along [100] induced by the surface effect; (iii) a hybrid improper FE state with the polarization along [110] that is induced by the trilinear coupling between two rotational modes and the A-site displacement. Interestingly, the ferroelectricity in the latter two cases becomes stronger along with decreasing the thin film thickness, in contrast to the usual behavior. Moreover, the latter two FE states are compatible with magnetism since their stability does not depend on the occupation of the d-orbitals of the B-ion. These two novel 2D FE mechanisms provide new avenues to design 2D multiferroics, as we demonstrated in SrVO and CaFeO thin film cases. Our work not only reveals new physical mechanisms of 2D ferroelectricity in perovskite oxide thin films but also provides a new route to design the high-performance 2D FE and multiferroics.

Li13Mn(SeO3)8: Lithium-Rich Transition Metal Selenite Containing Jahn-Teller Distortive Cations.

A novel lithium-rich transition metal selenite, Li13Mn(SeO3)8, that is composed of a Jahn-Teller distortive cation, Mn3+, in the high spin d4 state, and a second-order Jahn-Teller (SOJT) distortive lone pair cation, Se4+, has been synthesized via hydrothermal and high temperature solid state reactions. The selenite is classified as a molecular compound consisting of MnO6 octahedra, SeO3 trigonal pyramids, and Li+ cations. Considering the Li-O interactions, the structure of Li13Mn(SeO3)8 may be described as a pseudo-three-dimensional framework as well. The title compound is thermally stable up to 500 °C and starts decomposing above the temperature attributable to the volatilization of SeO2. While the MnO6 octahedra in Li13Mn(SeO3)8 exhibit six identical Mn-O bond distances at room temperature due to the dynamic Jahn-Teller effect, a clear elongation of two Mn-O bonds along a specific direction is observed at 100 K. A series of isostructural selenites with different transition metals, i.e., Li13M(SeO3)8 (M = Sc, Cr, and Fe), have been also successfully obtained in phase pure forms using similar synthetic methods. Magnetic properties, spectroscopic characterizations, and local dipole moments calculations for all the synthesized selenites are presented.

Thiophosphates Containing Ag+ and Lone-Pair Cations with Interchiral Double Helix Show Both Ionic Conductivity and Phase Transition.

Quaternary metal thiophosphates containing second-order Jahn-Teller distorted d10 Ag+ and lone-pair cations, Ag3Bi(PS4)2 (1), Ag7Sn(PS4)3 (2), and Ag7Pb(PS4)3 (3), were obtained by solid-state synthesis. The structural frameworks of 2 and 3 feature an infinite 1-D interchiral double helix ∞1(Ag3P2S11), which is rare in inorganic compounds. Compound 3 undergoes a significant first-order structural phase transition from monoclinic to hexagonal at ∼204 °C. This can be ascribed to the significant mismatch in the expansion coefficients between Pb-S (Ag-S) and P-S bonds evaluated by bond valence theory. The three compounds are Ag+ ionic conductors, and Ag+ ion migration pathways are proposed by calculating maps of low bond valence mismatch. Moreover, the optical properties of the three compounds were studied, and electronic structure calculations were performed. The combination of second-order Jahn-Teller distorted d10 cation and lone-pair cation provides a new strategy to explore new metal thiophosphates with interesting structures and promising properties.

Phase Transition and Second Harmonic Generation in Thiophosphates Ag2Cd(P2S6) and AgCd3(PS4)S2 Containing Two Second-Order Jahn-Teller Distorted Cations.

Two new phases in the Ag-Cd-P-S system containing two second-order Jahn-Teller (SOJT) distorted d10 cations (Cd2+ and Ag+), namely, Ag2Cd(P2S6) (1) and AgCd3(PS4)S2 (2), are obtained via medium-temperature solid-state synthesis. Compound 1 exhibits a two-dimensional layered structure and undergoes a first-order structural phase transition at approximately 280 °C. This outcome can be ascribed to the significant mismatch in the expansion coefficients between Cd-S (Ag-S) and P-P (P-S) bonds evaluated through bond valence theory. The three-dimensional non-centrosymmetric (NCS) framework of 2 is constructed by two types of tetrahedral layers consisting of corner-shared CdS4, AgS4, and PS4 tetrahedra. Compound 2 exhibits second harmonic generation (SHG) intensity of 0.45 times that of commercial AgGaS2 (AGS) at a laser irradiation of 1.85 μm and an optical band gap of 2.56 eV, and no intrinsic vibrational absorption of chemical bonds is observed in the range of 2.5-18.2 μm. Both phase transition in 1 and SHG properties in 2 are closely related to the SOJT distorted d10 cations and diverse phosphorus-sulfur polyanions (PaSb)n-, which together can easily result in NCS distorted structures and interesting properties.

"All-Three-in-One": A New Bismuth-Tellurium-Borate Bi3TeBO9 Exhibiting Strong Second Harmonic Generation Response.

A new nonlinear optical (NLO) material, Bi3TeBO9 (BTBO), is successfully grown from high temperature solution method. BTBO crystallizes in a polar space group of P63 with a framework structure composed of [Bi3O9] blocks, with TeO6 and BO3 interconnection. It is interesting that in the BTBO structure three types of NLO-active units, including stereochemically active lone pair cations (Bi3+ cations), second-order Jahn-Teller distorted octahedra (TeO6 octahedra) and π-orbital planar groups (BO3 groups), simultaneously exist. The additive contribution from these three types of groups results in an extremely large second harmonic generation (SHG) response in BTBO (about 20 times that of KDP), exhibiting the largest SHG effect among the known borate NLO materials. The enhancement of the nonlinear optical property is elucidated by the first-principles analysis.

Research progress of electrochromic performances of WO3

From the aspects of both experimental studies and first-principles calculation, we review the research progress of improving the electrochromic performances of WO3, and analyze the transformation tendency in applied field, performance requirement and research focus. Due to the low color-switching, the application field of WO3 shifts from display devices to smart windows or other energy-saving devices. According to the requirement for electrochromic performance, the concerned WO3 morphology changes from amorphous form to nanostructure. For the high desire of smart windows in large-area curtain walls, the solid state inorganic electrochromic materials with lithium ion conductors are used as substitutes for the organic electrochromic films in hydrogen ion electrolytic solution. Correspondingly, response time and cycle life are regarded as the most important performance indices. Doping and synthesizing nanostructure are considered to be the main methods to improve electrochromic performance by introducing the pores into the crystals as the ion diffusion path. Especially, the nano-crystalline WO3 attracts much attention, due to its high stability and quick color switching. In the respect of the first-principles calculation, the simple cubic WO3 is a widely used model for calculation, because of its simple structure and high symmetry. However, there always occur the underestimation of band gap and the incorrect relationship between the cell sizes of WO3 and LiWO3. In response to the problem, by analyzing the Li-intercalated WO3 configuration, it is found that the lattice parameter is closely associated with the interaction between lithium and oxygen. The large discrepancy between the experimental and calculated band gaps is primarily due to the omission of the structural distortion in the calculation, including tilting of WO6 octahedra, as well as the off-centering of W in octahedral caused by the second-order Jahn-Teller effect. According to this, we propose a distorted cubic WO3 model (Im3 space group) to better explain the relevant experimental results. In light of the achieved results and the encountered problems in recent researches, it is generally received that the industrialization of nano-crystalline WO3 and systematic calculation on the lithium diffusion in WO3 deserve the serious consideration. In addition, possessing the function of blocking near-infrared and visible light selectively is the trend for the next generation electrochromic materials. Therefore, the noteworthy development directions on the aspect of both experimental studies and first-principles calculation are pointed out to provide some valuable references for the further researches.

Tantalum and vanadium substitution in hexagonal K0.3WO3 bronze: synthesis and characterization

Abstract Polycrystalline samples of tantalum and vanadium single and double substituted hexagonal potassium tungsten bronzes (K-HTB’s) with nominal compositions of K0.3(W6+ 0.7W5+ 0.3–yTa5+ y)O3 (0≤y≤0.3), K0.3(W6+ 0.7W5+ 0.3–y V5+ y)O3 (0≤y≤0.18) and K0.3(W6+ 0.7W5+ 0.3–yTa5+ y/2V5+ y/2)O3 (0≤y≤0.3) were synthesized by solid state reactions in quartz tubes at 10–7 MPa and 1073 K. The applied synthesis condition allowed K0.3WO3 to crystallize in space group P6322, confirmed by X-ray powder diffration and Raman spectroscopic analyses. In this K-HTB composition, W5+ could fully be replaced by Ta5+, whereas V5+ could only be substituted up to y=0.16. The degree of W5+ substitution was explained in terms of second-order Jahn–Teller (SOJT) distortion of the d0 cations W6+, Ta5+ and V5+. The applied distortion index also demonstrates why a complete substitution of W5+ in K0.3(W6+W5+)O3 was allowed by a concomitant sharing of Ta5+ and V5+, which are statistically distributed on the W5+/W6+ sites. As W5+(d1) is not SOJT susceptible, it is also shown that the concentration of W5+ in tungsten bronzes plays an important role in the local WO6 octahedral symmetry as well as in its coordination.

Explorations of New SHG Materials in the Alkali-Metal-Nb(5+)-Selenite System.

Standard high-temperature solid-state reactions of NaCl, Nb2O5, and SeO2 resulted in two new sodium selenites containing a second-order Jahn-Teller (SOJT) distorted Nb(5+) cation, namely, Na2Nb4O7(SeO3)4 (P1̅; 1) and NaNbO(SeO3)2 (Cmc21; 2). Compound 1 exhibits an unusual 3D [Nb4O7(SeO3)4](2-) anionic network composed of 2D [Nb4O11(SeO3)2](6-) layers which are further bridged by additional SeO3(2-) anions via corner sharing; the 2D [Nb4O11(SeO3)2](6-) layer is formed by unusual quadruple [Nb4O17](14-) niobium oxide chains of corner-sharing NbO6 octahedra being further interconnected by selenite anions via Nb-O-Se bridges. The polar compound 2 features a 1D [NbO(SeO3)2](-) anionic chain in which two neighboring Nb(5+) cations are bridged by one oxo and two selenite anions. The alignments of the polarizations from the NbO6 octahedra in 2 led to a strong SHG response of ∼7.8 × KDP (∼360 × α-SiO2), which is the largest among all phases found in metal-Nb(5+)-Se(4+)/metal-Nb(5+)-Te(4+)-O systems. Furthermore, the material is also type I phase matchable. The above experimental results are consistent with those based on DFT theoretical calculations. Thermal stabilities and optical properties for both compounds are also reported.

ChemInform Abstract: New Quaternary Oxides with Both Families of Second‐Order Jahn—Teller (SOJT) Distortive Cations: Solid‐State Synthesis, Structure Determination, and Characterization of YNbTe2O8 and YNbSe2O8.

AbstractYNbTe2O8 (I) and YNbSe2O8 (II) are prepared by solid state reaction of Y2O3, Nb2O5, and TeO2 or SeO2 (evacuated silica tubes, 900 °C, 2 d; cooling to 600 °C with a rate of 6 °C/h).

New quaternary oxides with both families of second-order Jahn–Teller (SOJT) distortive cations: Solid-state synthesis, structure determination, and characterization of YNbTe2O8 and YNbSe2O8

Two novel quaternary mixed metal tellurite and selenite, YNbTe2O8 and YNbSe2O8, respectively, have been synthesized through standard solid-state reactions using Y2O3, Nb2O5, TeO2 or SeO2 as reagents. Single crystal X-ray and powder neutron diffraction analyses have been utilized to determine the structures of the reported materials. YNbTe2O8 and YNbSe2O8 are isostructural to each other and crystallize in the monoclinic centrosymmetric space group, C2/m (No. 12). Due to the two families of constituent second-order Jahn–Teller (SOJT) distortive cations, i.e., Nb5+ and Te4+/Se4+, local asymmetric environments occur from the three-dimensional frameworks. Intra-octahedral distortions along the local C4 direction and asymmetric trigonal pyramidal coordination moieties generated by stereoactive lone pairs are observed from the NbO6 octahedra and TeO3 (or SeO3) polyhedra, respectively. Thermogravimetric analysis, infrared and UV–vis diffuse reflectance spectroscopies, elemental analysis, out-of-center distortions, dipole moment calculations, and electronic structure calculations for the reported materials are presented.

Sr3Bi2(SeO3)6·H2O: A novel anionic layer consisting of second-order Jahn–Teller (SOJT) distortive cations

A new layered bismuth selenite hydrate material, Sr3Bi2(SeO3)6·H2O has been synthesized through a hydrothermal reaction using SrCO3, Bi2O3, SeO2, and water as reagents. The crystal structure of the reported material has been determined by single crystal X-ray diffraction analysis. The anionic layered framework of Sr3Bi2(SeO3)6·H2O consists of polyhedra of second-order Jahn–Teller (SOJT) distortive cations, Bi3+ and Se4+. Attributable to the variable and asymmetric coordination geometry of the constituent cations, a rich structural chemistry including uni-dimensional bands and linkers is observed in the layer. The material is thermally stable up to about 390°C and starts decomposing due to the sublimation of SeO2 above the temperature. The UV–vis diffuse reflectance spectrum suggests a band gap of 3.3eV. Elemental analysis, infrared spectrum, local dipole moment calculations, and electronic structure calculations are also reported.