Electric field amplification of plasmon-molecule hybrids revealed by first-principles time dependent density functional theory calculations

Using first-principles quantum mechanical calculations, we investigate the electric field amplification in hybrid nanostructures composed of few-atom Ni linear chains attached to an organic molecule. We found that the pristine Ni linear chains exhibit localized plasmons and produce nanoscale hotspot regions, acting as a plasmon-like nanoantenna. We demonstrate that localized plasmons provide massive electric field amplification in the vicinity of the molecule. Besides, we also investigated the active modulation of the optical absorption spectra due to the inclusion of a positive and/or negative electric field in the Hamiltonian. We believe that the results presented in this work are important for the emerging field of cavity induced photo-catalysis and will aid in the realization of new quantum nano-optic devices.     

A Three-Dimensional M3AB-Type Hybrid Organic–Inorganic Antiperovskite Ferroelectric: [C3H7FN]3[SnCl6]Cl

Since the first perovskite CaTiO₃ was discovered in 1839, the development of perovskite has a history of 180 years. The emergence of solar cells (CH₃NH₃)PbI₃ has set off the trend of hybrid organic–inorganic perovskite (HOIP) materials. Since then, various HOIPs have sprung up and been widely used in various material devices. Among them, HOIP ferroelectrics have gained widespread attention. However, antiperovskite, as a twin brother of perovskite, has been neglected although it has similar structure with perovskite. Here, we successfully found that [C₃H₇FN]₃[SnCl₆]Cl has a three-dimensional (3D) antiperovskite structure with the formula M₃AB. Importantly, the compound exhibits obvious ferroelectric properties with an Aizu notation of 622F6 at 391 K. To the best of our knowledge, this is the first 3D hybrid organic–inorganic antiperovskite ferroelectric, which will greatly promote the development of antiperovskite families with more superior physical properties.     

Hydrothermal synthesis,crystal structure and photoluminescent properties of 2D layered zinc phosphate intercalated with 4,4ˈbiphenyl dicarboxylic acid (ZnPO-BDA)

Herein, we report a new inorganic-organic hybrid, (H₃tren)₂?[Zn₃(PO₄)₄(BDA)]?xH₂O (ZnPO-BDA) prepared under hydrothermal conditions. This hybrid structure of zinc phosphate layers pillared with 4,4′-biphenyl-dicarboxylic acid (BDA) was characterized by single-crystal X-ray diffraction. The compound, ZnPO-BDA, crystallizes in the monoclinic crystal system (space group C2) with a = 14.9348(3) Å, b = 8.7058(2) Å, c = 17.6455(5) Å, β = 111.6760(10), V = 2132.02(9) ų, Z = 2. The crystalline host of the 2D zinc phosphate framework was built with vertex linked ZnO₄ and PO₄ tetrahedra and anchored with tris(2-aminoethyl)amine (H₃tren). Biphenyl dicarboxylic acid (BDA) molecules stack between the phosphate framework layers by means of strong hydrogen bonding, resulting in an interlayer distance of 16.4 Å. ZnPO-BDA displayed blue photoluminescence with an emission maximum at 404 nm on photoexcitation at 340 nm.     

Liquid‐Crystalline Biomacromolecular Templates for the Formation of Oriented Thin‐Film Hybrids Composed of Ordered Chitin and Alkaline‐Earth Carbonate

Macroscopically ordered inorganic thin films have been formed on unidirectionally oriented, liquid‐crystalline chitin matrices. In the presence of poly(acrylic acid) (PAA), unidirectionally oriented chitin films act as templates for the formation of oriented thin‐film crystals of alkaline‐earth carbonates such as SrCO₃ and BaCO₃. The morphology and orientation of crystals are dependent on the metal ion concentration. For SrCO₃ crystallization, unidirectional thin films and hexagonal‐shaped thin films have been deposited from 200 and 25 mm concentration strontium solutions, respectively.     

Field polarity dependent nucleation of superconductivity in quasi-one-dimensional magnetic templates

We investigate the nucleation of superconductivity in an Al/Al₂O₃/Py trilayer system by electrical transport measurements. Magnetic force microscopy images taken at room temperature show that the 0.7 μm thick Py-film form stripes of magnetic domains with alternating out-of-plane stray field. After applying a strong out of plane magnetic field H the superconductor/normal phase boundary becomes asymmetric with respect to H = 0. This lack of field polarity symmetry results from the unbalanced size distribution of domains with opposite polarity.     

Organic–inorganic hybrid membranes prepared from the sol–gel process of poly(butyleneadipate‐co‐terephthalate) and TiO2

Organic–inorganic hybrids based on poly(butyleneadipate‐co‐terephthalate)/titanium dioxide (PBAT/TiO₂) hybrid membranes were prepared via a sol–gel process. The PBAT/TiO₂ hybrid membranes were prepared for various PBAT/TiO₂ ratios. The resulting hybrids were characterized with a morphological structure, hydrophilicity, biodegradability, and thermal properties. The results showed that macrovoids underwent a transition into a sponge‐like membrane structure with the addition of TiO₂. After sol–gel transition, a strong interaction between the inorganic network and polymeric chains led to an increase in glass transition temperature (T_g), thermal degrading temperature, and hydrophilicity, and hence a higher biodegradability. According to X‐ray diffraction measurements of the crystal structure of the hybrid, the presence of TiO₂ did not change the crystal structure of PBAT. TiO₂ networks are uniformly dispersed into the PBAT matrix and no aggregation of TiO₂ networks in the hybrid membranes was observed through the small angle X‐ray scattering measurements. Thus, the sol–gel process of PBAT and TiO₂ can be used to prepare a hybrid with higher application temperature and faster biodegradation rate. Copyright © 2008 John Wiley & Sons, Ltd.     

Two Novel Organic–Inorganic Hybrid Compounds Constructed from Anderson-type Clusters and Transition-Metal Complexes

Abstract  Two organic–inorganic hybrid compounds based on the Anderson-type clusters [TeMo₆O₂₄]⁶⁻, [(H₂O)₂Co(TeMo₆O₂₄)][(C₁₀N₂H₁₀)₂] · 9.5H₂O (1), [(C₁₀N₂H₉)Ni(H₂O)₃]₂[TeMo₆O₂₄] · 8.5H₂O (2), have been synthesized by hydrothermal reactions and characterized by elemental analyses, IR spectra, thermal stability analyses, and single-crystal X-ray diffraction. Compound 1 displays a 1D chain structure constructed from alternating [TeMo₆O₂₄]⁶⁻clusters and Co²⁺ along the a axis with two pendant ligands 4,4′-bpy (4,4′-bipyridine). Compound 2 is composed of [TeMo₆O₂₄]⁶⁻ clusters coordinated by [Ni(bpy)(H₂O)₃]²⁺ moieties, and a supramolecular architecture is further formed through extensive hydrogen bonds interactions. Graphical Abstract  Two organic–inorganic hybrid compounds based on the Anderson-type clusters [TeMo₆O₂₄]⁶⁻and the unit [M(4,4′-bpy)] have been synthesized under the hydrothermal conditions. Compound 1 displays a 1D chain structure constructed covalently from alternating polyoxoanions [TeMo₆O₂₄]⁶⁻ and Co²⁺ along the a axis with two pendant ligands 4,4′-bipyridine. Compound 2 is composed of [TeMo₆O₂₄]⁶⁻ polyoxoanion coordinated by [Ni(bpy)(H₂O)₃]²⁺ moieties and shows a 1D chain structure through the hydrogen bonds interactions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis of Additives from Montmorillonite to Modify High Density Polyethylene Final Properties

Summary: This work brings about the modification of sodium montmorillonite clay (MNa) by the cationic exchange with hexadecyltrimethylammonium to turn it into organophilic clay (MC₁₆). Subsequently, MC₁₆ was treated with silanes. Three silanes with functional groups of different chemical nature were used. The objective was to determine if the clay could affect high density polyethylene (HDPE) final behavior after being modified with each silane. The following silanes were used: Cl₂Si(CH₃)₂, Cl₂Si(CH₃)(C₆H₅) and Cl₂Si(C₆H₅)₂. Finally, in situ hydrolysis was carried out to generate the respective siloxanes. These materials were characterized by XRD, FTIR and GPC analyses. Each one of these additives was mixed using melt compounding processing in a Haake torque rheometer Rheocord 9000 equipped with a mix chamber and roller rotors at 100 rpm and 190 °C. All hybrids were characterized by XRD, SEM and thermogravimetric analyses. Barrier properties to cyclohexane were also determined by pervaporation experiments. Results from all studies showed that the addition of approximately 3 wt% of clay has changed the macroscopic properties of the above-mentioned composites, as compared with pure HDPE. This can be explained considering the different polymer/filler interactions which take place in each system.     

Three inorganic-organic hybrids of bismuth(III) iodide complexes containing substituted 1,2,4-triazole organic components with charaterizations of diffuse reflectance spectra

The reactions of two kinds of substituted 1,2,4-triazoles with BiI₃ yielded three inorganic-organic hybrids: [HL1]₄[Bi₆I₂₂]·[L1]₄·4H₂O (1) (L1=3-(1,2,4-triazole-4-yl)-1H-1,2,4-triazole); [HL2]₄[Bi₆I₂₂]·6H₂O (2); [HL2]₂[Bi₂I₈]·[L2]₂ (3) (L2=(m-phenol)-1,2,4-triazole). Both 1 and 2 have polynuclear anions of [Bi₆I₂₂]^4- to build up the inorganic layers and substituted 1,2,4-triazoles as the organic layers. Hybrid 3 consists of two BiI₅ square pyramids as inorganic layers. There exist hydrogen bondings and I?I interactions in the structures of 1, 2 and 3. Optical absorption spectra of 1, 2 and 3 reveal the presence of sharp optical gaps of 1.77, 1.77 and 2.07 eV, respectively, suggesting that these materials behave as semiconductors.     

Polyoxometallates based macromolecules

The synthesis of polyoxometallates based macromolecules P _n (P=[SiW₁₁O₄₀(SiR)₂]^4–.4Bu₄N⁺) presenting interesting physical properties (electrochemistry, photochemistry) is detailed. Three different paths are described, organic polymerization of monomers P (R = vinyl, allyl, methacryl, styryl), hydrosilation of monomers (R=H, R=vinyl) or direct synthesis of polymeric species. These different polymers are characterized from a multi spectroscopic study (IR, NMR), and scattering experiments (QELS, SAXS). Reaction conditions influence both the polymerization yield, the size, the structure, and the properties of these organic-inorganic hybrids.