[C5H12N]SnCl3: A Tin Halide Organic–Inorganic Hybrid as an Above-Room-Temperature Solid-State Nonlinear Optical Switch

Nonlinear optical (NLO) switches driven by a solid-state structural phase transition have attracted extensive attention; however, above-room-temperature solid-state NLO switch materials are still sparse. Herein, we report an above-room-temperature tin halide organic–inorganic hybrid quadratic NLO switchable material, N-methylpyrrolidinium trichloride stannite ([C₅H₁₂N]SnCl₃, MPSC). The MPSC crystal exhibits a phase-matchable NLO property that is 1.1 times that of KH₂PO₄ (KDP) and NLO switching behavior, changing from a high second harmonic generation (SHG) response to a low SHG response at 383 K, thereby demonstrating its prospective applications in the field of nonlinear optics. Variable-temperature crystal structural analysis combined with theoretical calculations revealed that the large NLO response stems from the inorganic SnCl₃ moiety, whereas the high-performance NLO switching properties mainly originate from the order/disorder transformation of the N-methylpyrrolidinium. This work provides a new approach to designing and exploring new high-performance quadratic NLO switches involving tin halide organic–inorganic hybrids.     

Two 3D Rubidium Halide Organic–Inorganic Hybrid Perovskite Ferroelectrics Templated by Quasi-Spherical Organic Amine 1,4-Diazabicyclo[3.2.2]nonane

The emergence of (CH₃NH₃)PbI₃ has brought the development of three-dimensional (3D) organic-inorganic hybrid perovskite (OIHP) structures with ABX₃ type to a higher level; however, most 3D frameworks are constructed by corner-sharing of BX₆ octahedra. Herein, we substituted the spherical molecule 1,4-diazabicyclo[2.2.2]octane (2.2.2-dabco) with 1,4-diazabicyclo[3.2.2]nonane (1,4-3.2.2-dabcn) as a template to react with RbX (X=Br, I) in the corresponding HX acids under the consideration of reducing the molecular symmetry. Two 3D OIHP compounds [1,4-3.2.2-H₂dabcn]RbI₃⋅H₂O ( 1 ) and [1,4-3.2.2-H₂dabcn]RbBr₃ ( 2 ) crystallized in non-centrosymmetric point group mm2 before the phase transition point were isolated. Among them, the 3D inorganic framework of 1 is constructed by sharing the corner of [RbI₆] octahedra, while that of 2 is constructed by sharing the corner and face of [RbBr₆] octahedra to acquire large cavities to accommodate the organic amine cation [1,4-3.2.2-H₂dabcn]²⁺; this 3D framework type is unprecedented in the OIHPs. As expected, compounds 1 and 2 exhibit reversible phase transition, dielectric and second harmonic generation (SHG) and ferroelectric properties, in which the phase transition temperature of 2 at 374 K is much higher than compound 1 at 280 K.     

Complexation of N-Allyl Derivatives of Morpholinium with Copper(I) Halides: Synthesis and Crystal Structure of [C4H8ON(C3H5)2]+[Cu4Cl5]–, [C4H8ONH(C3H5)]+[CuBr2]–, and [C4H8ONH(C3H5)]+[CuBr1.41Cl0.59]–

The compounds [C₄H₈ON(C₃H₅)₂]⁺[Cu₄Cl₅]^– (I), [C₄H₈ONH(C₃H₅)]⁺[CuBr₂]^– (II), and [C₄H₈ONH(C₃H₅)]⁺[CuBr_1.41Cl_0.59]^– (III) were prepared for the first time by ac electrochemical synthesis from mono- and di-N-allyl derivatives of morpholinium and copper(I) halides in ethanol solution and structurally characterized. In the structure of I π-complex, the centrosymmetric Cu₈Cl₁₀ fragments are associated into layers perpendicular to the b axis. The N,N"-diallylmorpholinium cation functions as a bridge, which coordinates two copper atom of the adjacent inorganic fragments by both allyl groups. The trigonal-pyramidal surrounding of the Cu(I) atom, as well as the distorted tetrahedral coordination sphere of Cu(2), involves three chlorine atoms and the C=C bond, whereas the planar trigonal surrounding of the Cu(3) atom and trigonal-pyramidal surrounding of the Cu(4) atom involve only chlorine atoms. In the isostructural II and III σ-complexes, the edge-shared CuX₄ tetrahedra form the infinite copper-halide chains running along the a axis. The inorganic fragments and organic N-allylmorpholinium cations are united into the three-dimensional crystal structures by N–H···X and C–H···X (X = Cl, Br) hydrogen bonds.     

Phase transitions in (C7H12N2)2[SnCl6]Cl2·1.5H2O crystal,studied by NMR and infrared spectroscopy

The (C₇H₁₂N₂)₂[SnCl₆]Cl₂·1.5H₂O complex is a new member of the family of hybrid organic–inorganic perovskite compounds. It exhibits two order–disorder phase transitions with changes in the conformation of aromatic cations at the two transition temperatures 360 and 412 K. Differential scanning calorimetry, nuclear magnetic resonance (NMR), and Fourier-transform infrared (FT-IR) spectroscopy were used to investigate these phase transitions. These transition mechanisms were investigated in terms of the spin–lattice relaxation times T1 for ¹H static NMR and the chemical shifts for ¹³C CP–MAS. The temperature dependence of T1(¹H) and ¹³C chemical shifts are changed near T_C1 and T_C2. Furthermore, the splitting for ¹³C NMR signals in Phases (II) and (III) indicated a ferroelastic characteristic of the compound. In addition, FT-IR results indicate that the ordered conformational structure of aromatic cations undergoes a remarkable disorder with increasing temperature. The NMR and FT-IR studies suggest that the phase transition mechanisms are related to the reorientational motion of [C₇H₁₂N₂]²⁺ cations as a whole. Phase transition was examined in light of the interesting optical properties of this material.     

Organic–Inorganic Hybrid Material Based on Strandberg-Type Polyanion [Se2Mo5O21]4− and 2-Aminopyridine Ions

A new organic–inorganic hybrid compound (2-AMP)₄[Se₂Mo₅O₂₁]·2H₂O (1) [2-AMP = 2-aminopyridinium] has been synthesized and characterized by IR spectrum, UV–Vis spectra, ¹H NMR spectroscopy, thermogravimetric analyses, cyclic voltammetry measurements and single crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system with space group P-1 and a = 11.451(6) Å, b = 13.478(3) Å, c = 14.037(2) Å, α = 108.956(2)°, β = 96.260(2)°, γ = 97.174(3)°, Z = 2. The title compound contains four protonized 2-AMP cations, five distorted MoO6 octahedra and two SeO3 pyramids by sharing vertices and edges. These five Mo atoms are nearly coplanar, and two SeO3 pyramids lie on both sides of this plane. The interactions between [Se₂Mo₅O₂₁]^4? clusters are established through hydrogen contacts which involve selenium, water molecules and 2-aminopyridine cations to form a three-dimensional structure.     

Synthesis and Characterization of a Novel 3D Organic–Inorganic Hybrid Framwork Templated by Keggin Anions

A novel 3D compound, {K₃H₂[Cu(Gly)₂]₃BW₁₂O₄₀}·10H₂O 1 (Gly = glycine), has been synthesized and characterized by elemental analyses, IR, TG analyses, cyclic voltammetry, and single-crystal X-ray diffraction. Compound 1 contains square-grid layers constructed by potassium cations and copper-glycine coordination complexes, the [BW₁₂O₄₀]^4? anions as templates are accommodated in the square grids by connecting with the K atoms. The K atoms link [BW₁₂O₄₀]^4? anions from different layers together to yield a 3D novel structure. The crystal data for compounds 1: monoclinic, space group p2(1)/n, a = 18.832(4) Å, b = 16.488(3) Å, c = 20.570(4) Å, β = 106.21(3)°, V = 6133(2) Å³, Z = 4.     

Unusual Thermal Quenching of Photoluminescence from an Organic–Inorganic Hybrid [MnBr4]2−-based Halide Mediated by Crystalline–Crystalline Phase Transition

The ability to generate and manipulate photoluminescence (PL) behavior has been of primary importance for applications in information security. Excavating novel optical effects to create more possibilities for information encoding has become a continuous challenge. Herein, we present an unprecedented PL temporary quenching that highly couples with thermodynamic phase transition in a hybrid crystal (DMML)₂MnBr₄ (DMML=N,N-dimethylmorpholinium). Such unusual PL behavior originates from the anomalous variation of [MnBr₄]²⁻ tetrahedrons that leads to non-radiation recombination near the phase transition temperature of 340 K. Remarkably, the suitable detectable temperature, narrow response window, high sensitivity, and good cyclability of this PL temporary quenching will endow encryption applications with high concealment, operational flexibility, durability, and commercial popularization. Profited from these attributes, a fire-new optical encryption model is devised to demonstrate high confidential information security. This unprecedented optical effect would provide new insights and paradigms for the development of luminescent materials to enlighten future information encryption.     

（C5H7S2）3[Bi2Cl9）]的合成和晶体结构

标题化合物由ＢｉＣｌ３和乙酰丙酮在ＨＣｌ（气）／Ｃ２Ｈ５ＯＨ溶剂中通入Ｈ２Ｓ气体反应而得。晶体属四方晶系，Ｍｔ＝１１３０．７６，空间群Ｐ４１２１２。晶胞参数ａ＝ｂ＝８．８６７（２），ｃ＝４１．５１１（４）Ａ；Ｖ＝３２６４（１）Ａ＾３，Ｚ＝４，Ｄｃ＝２．３０ｇｃｍ＾－３，μ（ＭｏＫａ）＝１１８．６０７ｃｍ＾－１，Ｆ（０００）＝２１０４．晶结构由重原子法求得。最终偏离因子Ｒ＝０．０７２。晶体由分立的（     

Rb[C6H3(COOH)2(COO–)] · [C6H3(COOH)3] · 2H2O: Synthesis,Crystal Structure,and Properties

The salt Rb[C₆H₃(COO)₂(^–)] · [C₆H₃(COOH)₃] · 2H₂O (I) of trimesic acid was synthesized and its thermal stability and conductivity (10^–11 ohm^–1 cm^–1 at 298 K) were measured. Molecular and crystal structures of I were established by X-ray diffraction analysis. Hydrogen bonding system in complex I was detected by IR and Raman spectroscopies. X-ray diffraction data agree with vibration spectroscopy data.     

Copper complexes with N-allylisoquinolinium halides: Synthesis and crystal structures of [C9H7N(C3H5)]2CuIICl2.86Br1.14, [C9H7N(C3H5)CuIBr2] · H2O, and [C9H7N(C3H5)CuIBr2]

Crystals of the copper bromide complexes with N-allylisoquinolinium halides of the composition [C₉H₇N(C₃H₅)]₂Cu^IICl_2.86Br_1.14 (I), [C₉H₇N(C₃H₅)]Cu^IBr₂ · H₂O (II), and [C₉H₇N(C₃H₅)]Cu^IBr₂ (III) are prepared by ac electrochemical synthesis, and their structures are studied by X-ray diffraction analysis (DARCh-1 (for I) and KUMA/CCD (for II and III) diffractometers). The crystals of compound I are monoclinic: space group P2₁/n, a = 15.053(5) Å, b = 10.486(4) Å, c = 17.179(10) Å, γ = 109.77(3)°, V = 2552(4) ų, Z = 4. The crystals of complex II are triclinic: space group P $\overline 1 $ , a = 7.040(1) Å, b = 7.610(2) Å, c = 12.460(2) Å, α = 79.54(3)°, β = 86.73(3)°, γ = 89.51(1)°, V = 655.4(2) ų, Z = 2. The crystals of complex III are monoclinic: space group P2₁/n, a = 12.799(1) Å, b = 7.692(1) Å, c = 13.491(1) Å, β = 111.08(1)°, V = 1239.3(2) ų, Z = 4. The structure of compound I is built of the Cu^IIX ₄ ^2? tetrahedra and N-allylisoquinolinium cations united by the C-H···X contacts into corrugated layers. The crystal structure of π-complex II is formed of dimers of the composition [C₉H₇(C₃H₅)]₂ Cu ₂ ^I Br₄ forming layers in the direction of the z axis due to the C-H···X contacts. An important role in structure formation belongs to water molecules that cross-link the organometallic layers through the O-H···X contacts into a three-dimensional framework. When kept in the mother liquor for 6 months, the crystals of compound II transformed into crystals of compound III, whose structure consists of {[C₉H₇(C₃H₅)]₂Cu ₂ ^I Br₄} _n columns united through the C-H···Br contacts (H···Br 2.84(3)?2.92(4) Å) into a three-dimensional framework.     

配合物3AgNO3·2[C3H7S(CH2)2SC3H7]的晶体结构

本文测定了配合物3AgNO3·2BPrTE的晶体结构, 该晶体属三斜晶系, 空间各为PI,晶胞参数: a=0.8945(1), b=1.2355(2), c=1.3572(5)nm; α=98.69(2)°, β=92.74(2)°, γ=90.45(1)°; V=1.480nm^3; Z=2, 分子中三个Ag原子的配位数均为5, 但它们的配位多面体各不相同, Ag(3)为四方锥体, Ag(2)为三角双锥, Ag(1)则介于两者之间, NO3^-以单齿、不等长双齿和等长双齿两种形式配位于Ag原子。配体BPrTE也具有两种构象, 反式构象具有C1对称性, 并以两种形式和Ag原子配位, 偏转式构象不具有C4对称性, 与Ag原子形成五元螯合环, 分子为三维无限长链结构。     

Copper(I) hexafluorosilicateπ-complexes with allylammonium salts. Synthesis and crystal structure of [CuOOCH·C3H5NH3]2SiF6 and [Cu2Cl3·2C3H5NH3]2SiF6

Two novel copper (I) -complexes containing the SiF ₆ ^2– anion have been synthesized and studied by X-ray structure analysis. The crystals of the first title compound (A) are monoclinic, space group P2₁/b with a=13.039(5), b=10.586(4), c=6.072(2) Å, =100.23(2)°, and Z=2. The crystals of the second title compound (B) are triclinic, space group with a=14.495(5), b=7.633(2), c=6.429(8) Å, =90.67(8), =81.80(8), =94.05(3)°, and Z=1. In structure A, the copper cations and the bridge formiate anions form infinite [Cu(HCOO)]_n spirals, which are cross-linked due to the -interaction between copper and the double bond AA and the strong hydrogen bonds N–H... F(SiF ₆ ^2– ) to form a three-dimensional framework. In structure B, allylammonium similarly acts as a bridge linking the SiF ₆ ^2– and Cu₄Cl ₆ ^2– anions into layers.Lvov State University. Institute of Physical Chemistry, Ukrainian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 4, pp. 141–148, July–August, 1993.Translated by T. Yudanova     

Binary Complexes [M(NH3)5Cl][PdCl4] · H2O (M = Rh, Co): Crystal Structure of [Rh(NH3)5Cl][PdCl4] · H2O

Monohydrates of chloropentammine rhodium(III) and chloropentammine cobalt(III) tetracloropalladates(II) were synthesized. Single crystals of [Rh(NH₃)₅Cl][PdCl₄] · H₂O were obtained and studied by Xray diffraction. The crystallographic data are as follows: a = 7.8730(16) Å, b = 10.905(2) Å, c = 16.038(3) Å, = 102.70(3)°, V = 1343.3(5) ų, space group P2₁/c, Z = 4, d_calc = 2.422 g/cm³. The structure consists of alternating layers of [Rh(NH₃)₅Cl]²⁺ complex cations and [PdCl₄]^2- complex anions. Each anion layer contains two crystallographically independent Pd atoms, and the square coordination environment of one of these atoms is converted to a bipyramide. The structure of the compound [Co(NH₃)₅Cl][PdCl₄] · H₂O is determined and its unitcell parameters are refined: a = 7.813(3) , b = 10.896(4) , c = 15.966(5) , = 102.85(4)°, V = 1325.2(8) ³, and d_calc = 2.148 g/cm³. The synthesis temperature is shown to have an effect on the content of hydrated and anhydrous complexes in the mixture formed during precipitation of these binary salts from aqueous solutions.     

3D Organic–Inorganic Perovskite Ferroelastic Materials with Two Ferroelastic Phases: [Et3P(CH2)2F][Mn(dca)3] and [Et3P(CH2)2Cl][Mn(dca)3]

Organic–inorganic hybrid perovskite-type multiferroics have attracted considerable research interest owing to their fundamental scientific significance and promising technological applications in sensors and multiple-state memories. The recent achievements with divalent metal dicyanamide compounds revealed such malleable frameworks as a unique platform for developing novel functional materials. Herein, two 3D organic–inorganic hybrid perovskites [Et₃P(CH₂)₂F][Mn(dca)₃] ( 1 ) and [Et₃P(CH₂)₂Cl][Mn(dca)₃] ( 2 ) (dca=dicyanamide, N(CN)₂⁻) are presented. Accompanying the sequential phase transitions, they display a broad range of intriguing physical properties, including above room temperature ferroelastic behavior, switchable dielectricity, and low-temperature antiferromagnetic ordering (T_c=2.4 K for both 1 and 2 ). It is also worth noting that the spontaneous strain value of 1 is far beyond that of 2 in the first ferroelastic phase, as a result of the precise halogen substitution. From the point view of molecular design, this work should inspire further exploration of multifunctional molecular materials with desirable properties.     

Crystal structure and properties of H3[PMo12O40] · 3C2H6O

The title compound H₃[PMo₁₂O₄₀]· 3C₂H₆O was prepared and characterized by X-ray crystallography, its i.r. spectrum, cyclic voltammetry and e.s.r. spectra. The anion of the title compound is a Keggin-type heteropoly structure based upon a central PO₄ tetrahedron surrounded by 12 MoO₆ octahedra arranged in four groups of three edge-shared octahedra Mo₃O₁₃. Weak hydrogen bonds exist between the organic solvent molecules and the heteropoly anion. The catalytic activity of the title compound was determined by the synthesis of butyl acetate. The conversion of n-BuOH reached 93.3% and the yield of MeCO₂Bu-n was 92.0% when the ratio of MeCO₂H to n-BuOH, catalyst amount, reaction time, reaction temperature were 2:1, 0.24% of the reactants (50 mg), 2.0 h and 115 120 °C, respectively.     

Highly Conducting Organic–Inorganic Hybrid Copper Sulfides CuxC6S6 (x=4 or 5.5): Ligand-Based Oxidation-Induced Chemical and Electronic Structure Modulation

Conductive coordination polymers (CPs) have potential in a wide range of applications because of their inherent structural and functional diversity. Three electrically conductive CPs (Cu_xC₆S₆, x=3, 4 or 5.5) derived from the same organic linker (benzenehexathiol) and metal node (copper(I)) were synthesized and studied. Cu_xC₆S₆ materials are organic–inorganic hybrid copper sulfides comprising a π-π stacking structure and cooper sulfur networks. Charge-transport pathways within the network facilitate conductivity and offer control of the Fermi level through modulation of the oxidation level of the non-innocent redox-active ligand. Two Cu_xC₆S₆ (x=4 or 5.5) CPs display high electrical conductivity and they feature a tunable structural topology and electronic structure. Cu₄C₆S₆ and Cu_5.5C₆S₆ act as degenerate semiconductors. Moreover, Cu_5.5C₆S₆ is a p-type thermoelectric material with a ZT value of 0.12 at 390 K, which is a record-breaking performance for p-type CPs.