New organic‐pillared zincophosphate and interpenetrating‐layered zinc coordination polymer: Crystal growth on tarbuttite‐like sheets with surface‐active carboxylic acid groups

For the first time, crystal growth of two novel distinct structures is observed to emerge from parent tarbuttite‐like zincophosphate sheets, which feature uncoordinated carboxylic acid (─COOH) groups protruding on the surface. A prior study revealed that the ─COOH groups could be modified through mechanochemical reaction to alter the wettability of bulk solid. In this study, the modification of ─COOH groups via amidation in solutions was conducted to tune the wettability to more hydrophobic. A further study in the reactivity of the zincophosphate toward various organic amines resulted in crystal growth of two novel compounds, thereby, a 2D coordination polymer with parallel interpenetrating square lattice (sql) topology and a 3D framework of organopillared zincophosphate were discovered. Intriguing structure transformation involved disassembling and assembling of not only commonly seen molecular units but also zincophosphate polyhedra and clusters: in the former case from rare 5‐coordinate zinc to 4‐coordinate zinc, and in the latter case from original positively charged tarbuttite‐like ZnPO sheets to amine‐pillared neutral sheets composed of unique edge‐sharing Zn₂N₂O₄(H₂O)₂ dimers.     

The inorganic–organic hybrid zinc phosphite poly[(μ3‐hydrogen phosphito‐κ3O:O′:O′′)(piperidin‐1‐ium‐4‐carboxylate‐κO)zinc(II)]

A new inorganic–organic hybrid zinc phosphite, [Zn(HPO₃)(C₆H₁₁NO₂)]_n, has been synthesized hydrothermally. Protonated piperidin‐1‐ium‐4‐carboxylate (PDCA) was generated in situ by hydrolysis of the piperidine‐4‐carboxamide precursor. The P atom possesses a typical PO₃H pseudo‐pyramidal geometry. The crystal structure features an unusual (3,4)‐connected two‐dimensional inorganic zinc–phosphite layer, with organic PDCA ligands appended to the sheets and protruding into the interlayer region. Helical chains of opposite chirality are involved in the construction of a puckered sheet structure.     

An Interface‐Bridged Organic–Inorganic Layer that Suppresses Dendrite Formation and Side Reactions for Ultra‐Long‐Life Aqueous Zinc Metal Anodes

Aqueous zinc (Zn) batteries (AZBs) are widely considered as a promising candidate for next‐generation energy storage owing to their excellent safety features. However, the application of a Zn anode is hindered by severe dendrite formation and side reactions. Herein, an interfacial bridged organic–inorganic hybrid protection layer (Nafion‐Zn‐X) is developed by complexing inorganic Zn‐X zeolite nanoparticles with Nafion, which shifts ion transport from channel transport in Nafion to a hopping mechanism in the organic–inorganic interface. This unique organic–inorganic structure is found to effectively suppress dendrite growth and side reactions of the Zn anode. Consequently, the Zn@Nafion‐Zn‐X composite anode delivers high coulombic efficiency (ca. 97 %), deep Zn plating/stripping (10 mAh cm^?2), and long cycle life (over 10 000 cycles). By tackling the intrinsic chemical/electrochemical issues, the proposed strategy provides a versatile remedy for the limited cycle life of the Zn anode.     

Tetrahydroxy‐Perylene Bisimide Embedded in a Zinc Oxide Thin Film as an Electron‐Transporting Layer for High‐Performance Non‐Fullerene Organic Solar Cells

By introduction of four hydroxy (HO) groups into the two perylene bisimide (PBI) bay areas, new HO‐PBI ligands were obtained which upon deprotonation can complex Zn^II ions and photosensitize semiconductive zinc oxide thin films. Such coordination is beneficial for dispersing PBI photosensitizer molecules evenly into metal oxide films to fabricate organic–inorganic hybrid interlayers for organic solar cells. Supported by the photoconductive effect of the ZnO: HO‐PBI hybrid interlayers, improved electron collection and transportation is achieved in fullerene and non‐fullerene polymer solar cell devices, leading to remarkable power conversion efficiencies of up to 15.95 % for a non‐fullerene based organic solar cell.     

Organic–Inorganic Copolymerization for a Homogenous Composite without an Interphase Boundary

Ionic oligomers and their crosslinking implies a possibility to produce novel organic–inorganic composites by copolymerization. Using organic acrylamide monomers and inorganic calcium phosphate oligomers as precursors, uniformly structured polyacrylamide (PAM)‐calcium phosphate copolymer is prepared by an organic–inorganic copolymerization. In contrast to the previous PAM‐based composites by mixing inorganic components into polymers, the copolymerized material has no interphase boundary owing to the homogenous incorporation of the organic and inorganic units at molecular level, resulting in a complete and continuous hybrid network. The participation of the ionic binding effect in the crosslinking process can substantially improve the mechanical strength; the copolymer can reach a modulus and hardness of 35.14±1.91 GPa and 1.34±0.09 GPa, respectively, which are far superior to any other PAM‐based composites.     

New 3 D Tubular Porous Structure of an Organic–Zincophosphite Framework with Interesting Gas Adsorption and Luminescence Properties

A new 3D tubular zinc phosphite, Zn₂(C₂₂H₂₂N₈)_0.5(HPO₃)₂?H₂O ( 1 ), incorporating a tetradentate organic ligand was synthesized under hydro(solvo)thermal conditions and structurally characterized by single‐crystal X‐ray diffraction. Compound 1 is the first example of inorganic zincophosphite chains being interlinked through 1,2,4,5‐tetrakis(imidazol‐1‐ylmethyl)benzene to form a tubular porous framework with unusual organic–inorganic hybrid channels. The thermal and chemical stabilities, high capacity for CO₂ adsorption compared to that for N₂ adsorption, and interesting optical properties of LED devices fabricated using this compound were also studied.     

A two‐dimensional organic–inorganic hybrid perovskite‐type semiconductor: poly[(2‐azaniumylethyl)trimethylphosphanium [tetra‐μ‐bromido‐plumbate(II)]]

Recently, with the prevalence of `perovskite fever', organic–inorganic hybrid perovskites (OHPs) have attracted intense attention due to their remarkable structural variability and highly tunable properties. In particular, the optical and electrical properties of organic–inorganic hybrid lead halides are typical of the OHP family. Besides, although three‐dimensional hybrid perovskites, such as [CH₃NH₃]PbX₃ (X = Cl, Br or I), have been reported, the development of new organic–inorganic hybrid semiconductors is still an area in urgent need of exploration. Here, an organic–inorganic hybrid lead halide perovskite is reported, namely poly[(2‐azaniumylethyl)trimethylphosphanium [tetra‐μ‐bromido‐plumbate(II)]], {(C₅H₁₆NP)[PbBr₄]}_n, in which an organic cation is embedded in inorganic two‐dimensional (2D) mesh layers to produce a sandwich structure. This unique sandwich 2D hybrid perovskite material shows an indirect band gap of ～2.700 eV. The properties of this compound as a semiconductor are demonstrated by a series of optical characterizations and indicate potential applications for optical devices.     

Chitosan Bio‐Based Organic–Inorganic Hybrid Aerogel Microspheres

Recently, organic–inorganic hybrid materials have attracted tremendous attention thanks to their outstanding properties, their efficiency, versatility and their promising applications in a broad range of areas at the interface of chemistry and biology. This article deals with a new family of surface‐reactive organic–inorganic hybrid materials built from chitosan microspheres. The gelation of chitosan (a renewable amino carbohydrate obtained by deacetylation of chitin) by pH inversion affords highly dispersed fibrillar networks shaped as self‐standing microspheres. Nanocasting of sol–gel processable monomeric alkoxides inside these natural hydrocolloids and their subsequent CO₂ supercritical drying provide high‐surface‐area organic–inorganic hybrid materials. Examples including chitosan–SiO₂, chitosan–TiO₂, chitosan–redox‐clusters and chitosan–clay‐aerogel microspheres are described and discussed on the basis of their textural and structural properties, thermal and chemical stability and their performance in catalysis and adsorption.     

Reversible Light‐Driven Polymerization of Polyoxometalate Tethered with Coumarin Molecules

A new photosensitive polyoxometalate (POM) organic–inorganic hybrid compound has been prepared by covalently tethering coumarin moieties onto a Mn–Anderson cluster. This compound has been fully characterized by ¹H NMR, ¹³C NMR, FTIR, and UV/Vis spectroscopy, and ESI‐MS. This organic–inorganic hybrid compound can undergo reversible light‐driven polymerization and this process has been characterized in detail.     

Porous Zirconium–Phytic Acid Hybrid: a Highly Efficient Catalyst for Meerwein–Ponndorf–Verley Reductions

The utilization of compounds from natural sources to prepare functional materials is of great importance. Herein, we describe for the first time the preparation of organic–inorganic hybrid catalysts by using natural phytic acid as building block. Zirconium phosphonate (Zr‐PhyA) was synthesized by reaction of phytic acid and ZrCl₄ and was obtained as a mesoporous material with pore sizes centered around 8.5 nm. Zr‐PhyA was used to catalyze the mild and selective Meerwein–Ponndorf–Verley (MPV) reduction of various carbonyl compounds, e.g., of levulinic acid and its esters into γ‐valerolactone. Further studies indicated that both Zr and phosphate groups contribute significantly to the excellent performance of Zr‐PhyA.     

Dihydrogen phosphate mediated supramolecular frameworks in 2‐ and 4‐chloroanilinium dihydrogen phosphate salts

The title compounds, 2‐chloroanilinium dihydrogen phosphate (2CADHP) and 4‐chloroanilinium dihydrogen phosphate (4CADHP), both C₆H₇NCl⁺·H₂PO₄⁻, form two‐dimensional supramolecular organic–inorganic hybrid frameworks. In 2CADHP, the dihydrogen phosphate anions form a double‐stranded anionic chain generated parallel to the [010] direction through O—H...O hydrogen bonds, whereas in 4CADHP they form a two‐dimensional supramolecular net extending parallel to the crystallographic (001) plane into which the cations are linked through strong N—H...O hydrogen bonds.     

Oligothiophene Self‐Assembly on the Surface of ZnO Nanorods: Toward Coaxial p–n Hybrid Heterojunctions

We describe herein the design, synthesis and detailed structural characterization of hybrid 1D nanostructures. They are prepared by supramolecular self‐assembly of oligothiophene molecules on the surface of zinc oxide nanorods in solution at room temperature. Electronic absorption spectroscopy and X‐ray diffraction show that both organic and inorganic components in the coaxial p–n heterojunctions are crystalline. Especially, it is demonstrated that the organic compounds form a self‐assembled monolayer at the surface of the nanorods, which is not the case when zinc oxide quantum dots are instead used. As a result of their hybrid nature, the 1D nanostructures lead to ambipolar semiconducting nanostructured materials as active layers in field‐effect transistors.     

Assembly of two novel inorganic–organic hybrid solids based on 3-(aminomethyl)pyridine ligand

Two new inorganic–organic hybrids, (Hampy)Zn₂(PO₄) (HPO₃) (1) and (ampy)Zn₂(HPO₃)₂ (2), where ampy = 3-(aminomethyl)pyridine, have been solvothermally prepared and structurally characterized. Compound 1 exhibits an unusual two-dimensional layer structure, which possesses a central 4.8² zincophosphate sheet wrapped by infinite zincophosphite chains. Left- and right-handed helical chains participate in the formation of the zincophosphate layer. Compound 2 features a three-dimensional pillared-layer structure, in which two-dimensional Zn^II(HPO₃) inorganic sheets were cross-linked by ampy ligands. The simultaneous occurrence of zinc-amine helical chains in 2 is unique and, to the best of our knowledge, firstly encountered in phosphite/phosphate hybrid materials. Different coordination modes and roles of the same ampy ligand were observed in the formation of the hybrid structures.     

Synthesis and self‐assembly of tadpole‐shaped organic/inorganic hybrid poly(N‐isopropylacrylamide) containing polyhedral oligomeric silsesquioxane via RAFT polymerization

Aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS) was used to prepare a POSS‐containing reversible addition‐fragmentation transfer (RAFT) agent. The POSS‐containing RAFT agent was used in the RAFT polymerization of N‐isopropylacrylamide (NIPAM) to produce tadpole‐shaped organic/inorganic hybrid Poly(N‐isopropylacrylamide) (PNIPAM). The results show that the POSS‐containing RAFT agent was an effective chain transfer agent in the RAFT polymerization of NIPAM, and the polymerization kinetics were found to be pseudo‐first‐order behavior. The thermal properties of the organic/inorganic hybrid PNIPAM were also characterized by differential scanning calorimetry. The glass transition temperature (T_g) of the tadpole‐shaped inorganic/organic hybrid PNIPAM was enhanced by POSS molecule. The self‐assembly behavior of the tadpole‐shaped inorganic/organic hybrid PNIPAM was investigated by atomic force microscopy and dynamic light scattering. The results show the core‐shell nanostructured micelles with a uniform diameter. The diameter of the micelle increases with the molecular weight of the hybrid PNIPAM. Surprisingly, the micelle of the tadpole‐shaped inorganic/organic hybrid PNIPAM with low molecular weight has a much bigger and more compact core than that with high molecular weight. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7049–7061, 2008     

“Precipitation on Nanoparticles”: Attractive Intermolecular Interactions Stabilize Specific Ligand Ratios on the Surfaces of Nanoparticles

Confining organic molecules to the surfaces of inorganic nanoparticles can induce intermolecular interactions between them, which can affect the composition of the mixed self‐assembled monolayers obtained by co‐adsorption from solution of two different molecules. Two thiolated ligands (a dialkylviologen and a zwitterionic sulfobetaine) that can interact with each other electrostatically were coadsorbed onto gold nanoparticles. The nanoparticles favor a narrow range of ratios of these two molecules that is largely independent of the molar ratio in solution. Changing the solution molar ratio of the two ligands by a factor of 5 000 affects the on‐nanoparticle ratio of these ligands by only threefold. This behavior is reminiscent of the formation of insoluble inorganic salts (such as AgCl), which similarly compensate positive and negative charges upon crystallizing. Our results pave the way towards developing well‐defined hybrid organic–inorganic nanostructures.     

Epoxide Opening versus Silica Condensation during Sol–Gel Hybrid Biomaterial Synthesis

Hybrid organic–inorganic solids represent an important class of engineering materials, usually prepared by sol–gel processes by cross‐reaction between organic and inorganic precursors. The choice of the two components and control of the reaction conditions (especially pH value) allow the synthesis of hybrid materials with novel properties and functionalities. 3‐Glycidoxypropyltrimethoxysilane (GPTMS) is one of the most commonly used organic silanes for hybrid‐material fabrication. Herein, the reactivity of GPTMS in water at different pH values (pH 2–11) was deeply investigated for the first time by solution‐state multinuclear NMR spectroscopic and mass spectrometric analysis. The extent of the different and competing reactions that take place as a function of the pH value was elucidated. The NMR spectroscopic and mass spectrometric data clearly indicate that the pH value determines the kinetics of epoxide hydrolysis versus silicon condensation. Under slighly acidic conditions, the epoxy‐ring hydrolysis is kinetically more favourable than the formation of the silica network. In contrast, under basic conditions, silicon condensation is the main reaction that takes place. Full characterisation of the formed intermediates was carried out by using NMR spectroscopic and mass spectrometric analysis. These results indicate that strict control of the pH values allows tuning of the reactivity of the organic and inorganic moities, thus laying the foundations for the design and synthesis of sol–gel hybrid biomaterials with tuneable properties.     

Synthesis and Characterization of the New Lacunar Zincophosphate [C6H10N2][ZnP2O8H2]·0.6H2O

The new zincophosphate of chemical formula [C₆H₁₀N₂][ZnP₂O₈H₂] · 0.6H₂O was hydrothermally synthesized with p‐phenylenediamine as structure‐directing agent. The title compound crystallizes in the trigonal symmetry (proposed space group P3m1), where inorganic zincophosphate chains form layers due to the half occupancy of the unique crystallographic zinc site. The layers are separated from each other by p‐phenylenediammonium dications with hydrogen bonding scheme involving the ammonium protons that reveals a pillar‐like 3D structure aspect. The compound was characterized by powder X‐ray diffraction, multinuclear solid‐state NMR, scanning electron microscopy, chemical analysis, and thermogravimetric analysis.     

Water‐based inorganic/polymer hybrid particles prepared via a multiple miniemulsion process

A universal method for the synthesis of water‐based inorganic–polymer hybrid particles was developed in which no organic solvent is required. To demonstrate the versatility of this process, zinc phosphate, calcium carbonate, and barium sulfate were chosen as different pigment examples which additionally can be utilized for functional coating applications. Furthermore, a complex polymeric composition based on epoxy–acrylic–styrene was chosen to illustrate the versatility from a soft matter point of view. The overall synthesis process was carried out by coemulsification of two inverse miniemulsions, containing two precursors, surrounded with a polymerizable continuous phase. This was then transferred to a direct miniemulsion by addition to a surfactant solution and subsequent homogenization followed by radical polymerization of the vinylic monomers. To our knowledge, this is the first work where a polymerizable continuous phase has been used in an inverse miniemulsion formation followed by transfer to a direct miniemulsion, followed by polymerization, so that the result is a water‐based dispersion. The resultant dispersion was characterized by dynamic light scattering; the particles were investigated via transmission electron microscopy with in situ determination of crystallinity using electron diffraction. Elemental analysis was also performed for the particles and the polymerized miniemulsions using X‐ray fluorescence and inductively coupled plasma‐optical emission spectroscopy, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Organic–inorganic hybrid networks by the sol–gel process and subsequent photopolymerization

Organic–inorganic hybrid materials were prepared by a convenient two‐step curing procedure based on sol–gel condensation and subsequent photopolymerization. Novel bismethacrylate‐based hybrid monomers with pendant, condensable alkoxysilane groups were prepared by Michael addition and possessed number‐average molecular weights between 580 and 1600 g/mol. The formation of inorganic networks by sol–gel condensation of the alkoxysilane groups in the presence of aqueous methacrylic acid was monitored with rheological measurements. The condensation conversion was monitored with solid‐state ²⁹Si cross‐polarization/magic‐angle spinning NMR spectroscopy. Subsequent photopolymerization led to organic–inorganic hybrid networks and low volume shrinkage, ranging from 4.2 to 8.3%, depending on the molecular weight of the hybrid monomer applied. Highly filled composite materials with glass filler fractions greater than 75% showed attractive mechanical properties with Young's moduli of 2700–6200 MPa. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4274–4282, 2001     

Synthesis and characterization of UV‐curable phosphorus containing hybrid materials prepared by sol–gel technique

In this study, a series of ultraviolet (UV)‐curable organic–inorganic hybrid coating materials containing phosphorus were prepared by sol–gel approach from acrylate end‐capped urethane resin, acrylated phenyl phosphine oxide oligomer (APPO), and inorganic precursors. TEOS and MAPTMS were used to obtain the silica network and Ti:acac complex was employed for the formation of the titania network in the hybrid coating systems. Coating performance of the hybrid coating materials applied on aluminum substrates was determined by the analysis techniques, such as hardness, gloss, impact strength, cross‐cut adhesion, taber abrasion resistance, which were accepted by international organization. Also, stress–strain test of the hybrids was carried out on the free films. These measurements showed that all the properties of the hybrids were enhanced effectively by gradual increase in sol–gel precursors and APPO oligomer content. The thermal behavior of the hybrid coatings was investigated by thermogravimetric analysis (TGA) analysis. The flame retardancy of the hybrid materials was examined by the limiting oxygen index (LOI); the LOI values of pure organic coating (BF) increased from 31 to 44 for the hybrid materials containing phosphorus (BF‐P:40/Si:10). The data from thermal analysis and LOI showed that the hybrid coating materials containing phosphorus have higher thermal stability and flame resistance properties than the organic polymer. Besides that, it was found that the double bond conversion values for the hybrid mixtures were adequate in order to form an organic matrix. The polycondensation reactions of TEOS and MAPTMS compounds were also investigated by ²⁹Si‐NMR spectroscopy. SEM studies of the hybrid coatings showed that silica/titania particles were homogenously dispersed through the organic matrix. In addition, it was determined that the hybrid material containing phosphorus and silica showed fibrillar structure. Copyright © 2009 John Wiley & Sons, Ltd.