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.     

A 3D Aluminoborate Open Framework Interpenetrated by 2D Zinc–Amine Coordination‐Polymer Networks in Its 11‐Ring Channels

A new inorganic–organic hybrid solid, [Zn(dap)₂][AlB₅O₁₀], combining the structural features of 3D open‐framework inorganic solids and 2D metal–organic coordination polymers has been synthesized under solvothermal conditions. The compound displays extensive luminescence and moderate second‐harmonic‐generation efficiency.     

Poly[di‐μ3‐chloro‐μ2‐trans‐1,2‐di‐4‐pyridylethyl­ene‐dicopper(I)]: a two‐dimensional organic–inorganic hybrid constructed from linear CuCl clusters and bridging ligands

The structure of the title compound, [Cu₂Cl₂(C₁₂H₁₀N₂)]_n, contains infinite CuCl staircase‐like chains, which lie about inversion centres. The trans‐1,2‐di‐4‐pyrid­ylethyl­ene mol­ecules also lie about inversion centres and connect the CuCl chains through Cu—N coordination bonds into a two‐dimensional organic–inorganic hybrid network. The planar sheets are stacked along the c axis and associated through weak C—H⋯Cl inter­actions. The results show a reliable structural motif with controllable separation of the CuCl chains by variation of the length of the ligand.     

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.     

Poly[bis­[2‐(1‐cyclo­hexen­yl)ethyl­ammonium] di‐μ‐iodo‐diodo­plumbate(II)]

The title compound, (C₈H₁₆N)₂[PbI₄], crystallizes as an inorganic–organic hybrid perovskite, adopting the unusual 2a_p× 2a_p superstructure. As such, the structure consists of two‐dimensional sheets of corner‐sharing PbI₆ octa­hedra in the ab plane, separated by bilayers of 2‐(1‐cyclo­hexen­yl)ethyl­ammonium cations. The ethyl­ammonium groups are not in the plane of the cyclo­hexenyl rings.     

A 3D Iodoplumbate Semiconducting Open Framework with Visible‐light‐induced Photocatalytic Performance

Employing in situ N‐alkylation of the conjugated compound 9,10‐bis(4‐pyridyl)anthracene (bpanth) as structure‐directing agent, a 3D inorganic‐organic hybrid iodoplumbate, [Me₂(bpanth)][Pb₄I₁₀] ( 1 ), was solvothermally prepared. The in situ N‐alkylation of bpanth with alcohols was investigated. 1 features a novel 3D open framework based on an interesting Pb₆I₂₄ cluster. UV/Vis spectroscopy analyses indicate that 1 is a potential semiconductor material with a narrow energy gap of 2.06 eV. It exhibits good catalytic activity in the visible‐light‐drived degradation of an organic dye. This work further illustrates that introducing conjugated organic molecules as templates is conducive to achieving semiconducting hybrid halometallates with narrow band gaps.     

An Organic‐Inorganic Hybrid Based on Keggin‐Type Polyoxometalate and Hypoxanthine: Synthesis,Structure, Stability,and Electrochemistry Properties

The organic‐inorganic hybrid H₅[Ag₂(hyp)₂]₂[BW₁₂O₄₀] · 9H₂O ( 1 ) (hpy = hypoxanthine), based on Keggin‐type polyoxometalate and hypoxanthine, was prepared by hydrothermal synthesis and characterized by single‐crystal and powder X‐ray diffraction, IR spectroscopy, elemental analysis, and thermogravimetry. The title compound has a two‐dimensional layer structure constructed by Keggin‐type [BW₁₂O₄₀]^5– anion, silver, and the biomolecule hyp. In addition, compound 1 exhibited excellent stability and superior activity in the electro‐catalytic oxidation of glucose.     

Pentane‐1,5‐diaminium dibromide

The crystal structure of the title salt, C₅H₁₆N₂²⁺·2Br⁻, with Z = 12 and more unusually Z′ = 3, forms part of a small group of crystal structures in the Cambridge Structural Database that are ammonium bromide salts. One of the diaminium cation chains in the asymmetric unit exhibits positional disorder, which was modelled using a suitable disorder model. This compound also exhibits organic–inorganic layering in its packing arrangement that is typical of this class of compound. An extensive complex three‐dimensional hydrogen‐bonding network is also identified. The hydrogen bonds evident in this crystal structure were identified as being most likely strong charge‐assisted hydrogen bonds.     

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.     

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.     

catena‐Poly[tetra­kis(3‐phenyl­propyl­ammonium) [iodo­plumbate(II)‐tri‐μ‐iodo‐plumbate(II)‐tri‐μ‐iodo‐iodo­plumbate(II)‐di‐μ‐iodo]]

The title compound, {(C₉H₁₄N)₄[Pb₃I₁₀]}_n, crystallizes as an organic–inorganic hybrid. As such, the structure consists of a two‐dimensional inorganic layer of [Pb₃I₁₀]_n⁴ⁿ⁻ ions extending along [100]. The asymmetric unit contains two independent Pb atoms, viz. one in a general position and the other on an inversion centre. Each Pb atom is octa­hedrally coordinated by six iodide ions and exhibits both face‐ and corner‐sharing with adjacent atoms in the inorganic layer. These anionic layers alternate with 3‐phenyl­propyl­ammonium cations, which hydrogen bond to the iodides. Simple face‐to‐edge σ–π stacking inter­actions are observed between the aromatic rings that stabilize the overall three‐dimensional structure. This net structure has only been observed five times previously.     

Zero‐Dimensional Hybrid Cd‐Based Perovskites with Broadband Bluish White‐Light Emissions

Recently, low‐dimensional organic‐inorganic hybrid metal halide perovskites acting as single‐component white‐light emitting materials have attracted extensive attention, but most studies concentrate on hybrid lead perovskites. Herein, we present two isomorphic zero‐dimensional (0D) hybrid cadmium perovskites, (HMEDA)CdX₄ (HMEDA=hexamethylenediamine, X=Cl ( 1 ), Br ( 2 )), which contain isolated [CdX₄]^2? anions separated by [HMEDA]²⁺ cations. Under UV light excitation, both compounds display broadband bluish white‐light emission (515 nm for 1 and 445 nm for 2 ) covering the entire visible light spectrum with sufficient photophysical stabilities. Remarkably, compound 2 shows a high color rendering index (CRI) of 83 enabling it as a promising candidate for single‐component WLED applications. Based on the temperature‐dependent, powder‐dependent and time‐resolved PL measurements as well as other detailed studies, the broadband light emissions are attributed to self‐trapped excitons stemming from the strong electron‐phonon coupling.     

Octa­kis(3‐propyl­ammonium) octa­deca­iodo­penta­plumbate(II): a new layered stucture based on layered perovskites

The title compound, (C₃H₁₀N)₈[Pb₅I₁₈], crystallizes as an inorganic–organic hybrid. As such, the structure consists of two‐dimensional sheets of corner‐ and face‐sharing [PbI₆]⁴⁻ octa­hedra, separated by layers of 3‐propyl­ammonium cations, which hydrogen bond to the I atoms. The asymmetric unit contains six independent Pb atoms; four are on general positions and the other two are on special positions, viz. a centre of inversion and a twofold axis. The inorganic sheets show a never before seen motif.     

Redox‐Controlled Helical Self‐Assembly of a Polyoxometalate Complex

Polyoxometalate (POM) complex (DODA)₂[Mo₆O₁₉] with a symmetrical linear structure was prepared conveniently by replacing the tetrabutylammonium (TBA) counterions of Lindquist‐type cluster (TBA)₂[Mo₆O₁₉] with cationic surfactant dioctadecyldimethylammonium (DODA). A helical self‐assembled structure of the complex was formed in dichloromethane/propanol. The dynamically reversible transformation between helical and spherical assemblies on alternate UV irradiation and H₂O₂ oxidation was characterized by SEM, TEM, and UV/Vis studies. The redox‐controlled morphology change is modulated by variation of the electrostatic interactions between the inorganic polyanion and the organic cation DODA through controlling the redox properties of the POM component, as shown by the XRD, X‐ray photoelectron spectroscopic, and ¹H NMR measurements. The strategy applied herein is a unique example of targeted smart and helical assembly of POM complexes.     

catena‐Poly[bis­(tert‐butyl­ammonium) [plumbate(II)‐tri‐μ‐iodo] iodide dihydrate]

The title compound, {(C₄H₁₂N)₂[PbI₃]I·2H₂O}_n, crystallizes as an organic–inorganic hybrid. The six‐coordinate Pb atom lies on a centre of inversion and all the I atoms lie on mirror planes; the two independent cations both lie across mirror planes. The structure contains anionic chains along [100] of fused [PbI₃]⁻ units forming face‐sharing octa­hedra. Four cations enclose channels occupied by isolated iodide ions and water mol­ecules of hydration.     

Solvothermal Synthesis,Crystal Structure and Properties of the First Organic‐templated Holmium Sulfate [C2N2H10]3[Ho2(SO4)6·2H2O]

The first organic amine‐templated holmium sulfate [C₂N₂H₁₀]₃[Ho₂(SO₄)₆·2H₂O] ( 1 ) has been synthesized solvothermally and has been structurally characterized by single‐crystal X‐ray diffraction studies, IR spectroscopic, thermogravimetric (TG) and inductivity coupled plasma (ICP) measurements. Crystal analyses of compound 1 showed a novel inorganic layer constructed from the zigzag and helical [–Ho–O–S–O–]_n chains, both of the chains are connected by μ‐2 SO₄^2– groups to form 10‐membered rings. The solvent plays an important role during the formation of 1 .     

In situ Alkylation of 4,4′‐Vinylenedipyridine for Inorganic‐Organic Iodides/Iodidomercurates

Solvothermal reactions of HgI₂, 4,4′‐vinylenedipyridine, and HI in alcoholic solution (methanol, ethanol, or pentanol) gave rise to a family of organic‐inorganic hybrid complexes, formulated as [C₁₄H₁₆N₂][I₄]^2– ( 1 ), [C₁₆H₂₀N₂][HgI₄] ( 2 ), and [C₂₂H₃₂N₂][HgI₄]₄ ( 3 ). Single‐crystal X‐ray diffraction reveals that all three compounds are discrete structures, including the inorganic anion [I₄]^2– or [HgI₄]^2– and an organic cation, where the resulting organic cations were generated in situ alkylation reactions of 4,4′‐vinylenedipyridine with alcohols, with cleavage of the alcoholic C–O bond followed by a one‐step in situ N‐alkylation reaction of 4,4′‐vinylenedipyridine in acidic HI solution. X‐ray powder diffraction (XRD), ¹H NMR and ¹³C NMR, energy‐dispersive X‐ray (EDS), IR, as well as UV/Vis/NIR spectroscopy, elemental analysis, and thermogravimetric analysis (TGA) were used to characterize the complexes.     

Solid polymer electrolytes. VI. Microstructure of organic–inorganic hybrid networks composed of 3‐glycidoxypropyltrimethoxysilane and LiClO4 and affected by different synthetic routes

Hybrid organic–inorganic materials derived from 3‐glycidoxypropyltrimethoxylsilane were prepared via two different synthetic routes: (1) the HCl‐catalyzed sol–gel approach of silane followed by the lithium perchlorate (LiClO₄)/HCl‐catalyzed opening of epoxide and (2) the simultaneous gelation of tin/LiClO₄‐catalyzed silane/epoxide groups. LiClO₄ catalyzed the epoxide polymerization, and its effects on the structures of these hybrid materials were studied by NMR. The structure of the inorganic side was probed by solid‐state ²⁹Si NMR spectroscopy, and the characterizations of the organic side and the chemical processes involved in the different synthetic routes were performed with solid‐state cross‐polarity/magic‐angle‐spinning ¹³C NMR. The different synthetic routes significantly affected the polymerization behaviors of the organic and inorganic sides in the presence of LiClO₄. A larger amount of LiClO₄ promoted the opening of epoxide and led to the formation of longer poly(ethylene oxide) chains via the HCl‐catalyzed sol–gel approach, whereas in the case of the tin‐catalyzed approach, the faster polymerization of the inorganic side hindered the growth of the organic network. The addition of LiClO₄ was proven to be without crystalline salt present in the hybrid networks by wide‐angle X‐ray powder diffraction. Also, the interactions between the ions and hybrid host, examined with Fourier transform infrared and ⁷Li proton‐decoupled magic‐angle‐spinning NMR, further demonstrated that extensive ion aggregation existed in these hybrid materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 151–161, 2004     

Synthesis of Multifunctional Metal‐ and Metal Oxide Core@Mesoporous Silica Shell Structures by Using a Wet Chemical Approach

We demonstrate a facile wet chemical approach for fabricating spherical metal/metal‐oxide core@mesoporous silica shell hybrid nanoparticles with different core and shell thicknesses. Vertically aligned mesoporous silica (mSiO₂) shells were fabricated over the pre‐synthesized spherical SiO₂ nanoparticles through a three‐step strategy: 1) synthesis of core materials, 2) covering the core with an organic–inorganic composite layer, and 3) removing the organic template through calcinations in air. The mechanisms of hybrid structure formation are proposed. The multifunctional nature of the hybrid structures could be induced by incorporating guest ions/molecules, such as Ag, Mn, and TiO₂, into the pores of an mSiO₂ shell. Mn and TiO₂ cluster‐ incorporated composite structures have been tested to be antioxidizing agents and effective photocatalysts through electron spin resonance, radical scavenging tests, and the photocatalytic degradation of rhodamine B. The possibility of incorporating several hetero‐element guest clusters in these mesoporous composite particles makes them highly attractive for multifunctional applications.     

1D Polyoxometalate‐based Inorganic‐Organic Hybrid Derived from ß‐Octamolybdate — Synthesis and Crystal Structure of [CoII(2, 2′‐bipy)2]2[Mo8O26]

A polyoxometalate‐based inorganic–organic hybrid compound [Co^II(2, 2′‐bpy)₂]₂[Mo₈O₂₆] ( 1 ) was synthesized by hydrothermal methods and structurally characterized by IR spectrum, TG analysis and X‐ray diffraction. The compound crystallizes in the monoclinic system, space group P2₁/n, a = 10.0681(2), b = 16.4467(2), c = 15.7838(3) Å, β = 100.046(1)°, V = 2573.52(8) ų, Z = 2. The structure of 1 is built up from β‐[Mo₈O₂₆]^4? subunits covalently linked via [Co^II(2, 2′‐bpy)₂]²⁺ fragments into a infinite 1D {[Co^II(2, 2′‐bpy)₂]₂[Mo₈O₂₆]}_∞ polymer.