Iodide Chains Research Articles

Effect of structural evolution and orientation behavior on optical properties of iodine-dyed PVA film during uniaxial stretching

In the process of preparing polarizing film, based on the research on the influence of the initial condensed structure of Poly (vinyl alcohol) (PVA) film on the dyeing and stretching process, the connection between the structure and performance of polarizing film is established, which is more conducive to understanding the post-processing process of solution casting molding of optical grade PVA film and the optimization of subsequent dyeing and stretching process. In this paper, PVA film with an appropriate swelling degree were selected for dyeing treatment, and the evolution of the condensed structure during stretching was studied in detail. The work also examined the formation and orientation of PVA-iodine complexes and the feedback effect of complex formation on the structural evolution of the film, with the goal of establishing the relationship between stretching ratio, structure, and performance of the polarizing film. The results show that the dyeing process inhibits the recrystallization of the PVA film during uniaxial stretching. However, the PVA-iodine complexes formed act as "anchors" to stabilize the oriented microfiber network, reducing the critical strains (εw and εs) required for the PVA film to enter the strain-hardening zone. Furthermore, as strain increases, the content of polyiodide ions and PVA-iodine complexes in the dyed PVA film also increases, especially making the formation of long iodide chains (I5−) and PVA-I5− complex more sensitive. Additionally, with increasing strain, both the transmittance and degree of polarization of the dyed PVA film improve, reaching optimal values in the strong strain-hardening zone (>εs). This indicates that εs is the minimum critical strain required to ensure optimal polarization performance of the film in the visible light region.

Design, synthesis, structure analysis and photophysical characterization of robust and solution-processable one-dimensional copper(I) iodide-based inorganic-organic hybrid semiconductors

A series of new one-dimensional (1D) CuI-based inorganic-organic hybrid semiconductors have been designed and synthesized, namely, 1D-(dmpi)3Cu6I9 (1), 1D-(5asn)2Cu4I6 (2), 1D-(Nhex)2Cu4I6 (3) and 1D-(Npipz)2Cu2I6 (4) (dmpi = N,N-dimethylpiperidinium, 5asn = 5-azaspiro[4.4]nonan-5-ium, Nhex = cyclohexanaminium, Npipz = 1-methylpiperazine-1,4-diium). All structures are composed of ionically bonded aliphatic cations and various 1D CuI anionic copper iodide chains. Due to their wide bandgaps, all materials display ultraviolet (UV) emission between 340 and 390 nm, with internal quantum yields (IQYs) up to 6.4 %. All compounds are solution-processable due to their ionic bonding nature and have excellent thermal stability with their decomposition temperature (Td) up to 260 °C, as well as impressive air stability over long time periods. Due to the use of aliphatic cations as structure directing agents, the photophysical properties of these materials are dominated by their inorganic components, as confirmed by electronic structure calculations employing density functional theory (DFT). Additionally, their non-toxicity and facile synthesis suggest that this type of material is promising for practical use. These findings provide helpful insight into the future development of high-performance wide bandgap semiconductors that may be potentially useful in various UV-emitting or other optoelectronic applications.

Bi3+ doping in 1D ((CH3)3SO)PbI3: a model for defect interactions in halide perovskites

Defect interactions and short-range ordering determine the bandgap reduction in linear lead/bismuth iodide chains.

A New Type of Hybrid Copper Iodide as Nontoxic and Ultrastable LED Emissive Layer Material

Perovskite-based light-emitting diodes (PeLEDs) are promising candidates for next-generation solid-state lighting and display technologies. However, all current high-performance PeLEDs contain a toxic element (lead) and suffer from relatively low stability. Herein, we report a new type of lead-free LED using low-cost, eco-friendly, and robust copper(I) iodide hybrid material as the emissive layer (EML). Specifically, they are composed of copper iodide chains and organic ligands through ionic and coordinate bonds. Their remarkable stability and solution processability stem from this unique multifold bonding feature. High-quality thin films of 1D-Cu4I6(bttmp)2 were fabricated by a simple, one-step spin-coating process. They exhibit high photoluminescence quantum yield (91%) and long-term air stability (>2000 h). An EQE of 5.02% was achieved for a prototype yellow LED using 1D-Cu4I6(bttmp)2 EML. Its half-lifetime of 35.5 h obtained in open air outperforms that of most PeLEDs reported to date. This work opens a new direction for making LEDs based on ecofriendly and robust hybrid materials.

Effects of different wavelength from Light Emitting Diodes (LEDs) on growth and development in zebrafish (Danio rerio) embryos and larvae

A light environment in aquatic habitat is one of the essential physical parameters affecting the growth and physiology of fish. To investigate the effects of light on the growth of zebrafish embryos and larvae (Danio rerio), fishes were reared under the illumination of Light Emitting Diodes (LEDs) of different wavelengths, including green, red, blue, and white. Morphometric, neuromast staining with 2-[4-(Dimethylamino)styryl]-1-ethylpyridinium iodide (DASPEI) and Polymerase Chain Reaction (PCR) analyses were used to examine the initial development of sensory capacity in this study. On days 5, 6, and 7, the green light produced the most favorable result. Blue light consistently impacted early parameters such as eye development, egg yolk absorption, and total length. These impacts were synchronous with the initiation of feeding. Exposure to specific wavelengths of light can induce the appearance of gene expression, opn1lw1 detected opsin and (mtnr1ba and aanat2) were active under all four experimental lighting conditions. This retinal gene appears to be sensitive to ambient wavelength, but apparently, genes in the melatonin pathway are not.

Preparation of perovskite-derived one dimensional single crystals based on edge-shared octahedrons with pyridine derivatives

Single crystals of hybrid materials based on 1D lead iodide perovskite networks with two pyridine (Py) derivatives, namely 4-ethyl (4Et)Py and 4-aminomethyl (4AM)Py, have been prepared. The compounds assembled into edge-shared lead iodide chains that formed needle-shaped crystals with lengths greater than 1 cm. The crystal containing (4Et)Py formed in the triclinic system with P1 symmetry. The molecules were stacked along with the novel triple chain of 1D perovskite-derived networks. The crystal containing 4AMPy formed in the monoclinic system with P21/a symmetry. The amino group formed hydrogen bonds to iodide anions. The optical band gaps for the 4EtPy-based and 4AMPy-based crystals were estimated to be 2.73 eV and 2.64 eV, respectively. The slight difference between the functional groups of the two molecules governed their crystal structures and hence optical properties.

Three New Lead Iodide Chain Compounds, APbI3, Templated by Molecular Cations

The crystal structures of three new hybrid organic-inorganic lead halide compounds [IqH]PbI3, [4MiH]PbI3, and [BzH]PbI3 ([IqH+] = isoquinolinium, [4MiH+] = 4-methylimidazolium, [BzH+] = benzotriazolium) have been determined by single crystal x-ray diffraction. All three compounds have the same generic formula as perovskite, ABX3, but adopt a rare non-perovskite structure built from one dimensional (1D) edge-sharing octahedral chains. The bandgap of each compound was investigated by solid UV-Vis spectra. In comparison with previously reported hybrid compounds containing the same type of octahedral chains, [C10H7CH2NH3]Pbl3 and (C7H7N2)PbI3, all three new compounds have lower bandgaps (<2.4 ev), indicating that they may be promising for photovoltaic application.

A fluorescence quenching sensor for Fe3+ detection using (C6H5NH3)2Pb3I8·2H2O hybrid perovskite

A new organic-inorganic hybrid perovskite (C6H5NH3)2Pb3I8·2H2O single crystal has been synthesized through a facile solution method. In this perovskite, there exists a 1D infinite lead iodide chains constituted by Pb3I8 groups, which is surrounded by anilines. As an active fluorescence quenching sensor material, this perovskite shows excellent performance for Fe3+ detection in N, N-dimethylformamide (DMF) solution with a detection limit of 1.0 × 10−7 mol/L, including short response time, high sensitivity and high selectivity. The sensitivity and selectivity towards Fe3+ is much higher than that towards other metal cations, which provides a facile way for detecting Fe3+ cations in solution. Electron paramagnetic resonance (EPR) confirms that the mechanism of fluorescence quenching can be attributed to Fe3+ inhibition to the radiative electron-hole recombination via capturing electrons.

3D Inorganic Cuprous Iodide Open-Framework Templated by In Situ N-Methylated 2,4,6-Tri(4-pyridyl)-1,3,5-triazine

A novel 3D inorganic cuprous iodide framework templated by in situ N-methylated 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPT) was solvothermally prepared and structurally characterized. The title compound bearing chiral cuprous iodide chains as building units is the first 3D extended framework with the TPT-derivatives as template. The UV–vis diffuse-reflectance measurement reveals that 1 possesses semiconductor behavior with band gaps of 1.35 eV. The photoluminescent property of 1 has also been studied.

Polyiodide chains resolve starch test mystery

In the course of developing new semiconducting materials, a research team including Ram Seshadri and Fred Wudl of the University of California, Santa Barbara, has solved a historical puzzle regarding the structure of the starch-iodine complex (Angew. Chem. Int. Ed. 2016, DOI: 10.1002/anie.201601585). Iodine dissolved in potassium iodide solution has long been used as a test for the presence of starch. The helical iodide chain that forms wraps around starch molecules (amylose) to create a complex that produces a deep purple color. Although scientists have speculated that polymeric iodide chains are involved, the exact structure has remained elusive. Chemists have reported other organic polyiodide complexes, but when characterized they have been found to have chain lengths shorter than 10 iodide units and contain molecular iodine (I2) within the chain. The perylene-iodine complex, for example, made up of stacks of the planar polycyclic aromatic hydrocarbon perylene interspersed with iodide strands, was

Inside Back Cover: Infinite Polyiodide Chains in the Pyrroloperylene–Iodine Complex: Insights into the Starch–Iodine and Perylene–Iodine Complexes (Angew. Chem. Int. Ed. 28/2016)

Inside Back Cover: Infinite Polyiodide Chains in the Pyrroloperylene–Iodine Complex: Insights into the Starch–Iodine and Perylene–Iodine Complexes (Angew. Chem. Int. Ed. 28/2016)

(Invited) Hybrid Organic/Inorganic Bismuth-Based Materials for Solution-Processed Thin-Film Photovoltaics

The lead–halide-based hybrid organic–inorganic perovskite material, methylammonium lead iodide (MAPbI3), has recently garnered increased attention among researchers worldwide as a promising photovoltaic material. As of 2015, perovskite photovoltaic devices have achieved laboratory efficiencies in excess of 20%. Many challenges regarding the stability and toxicity of the MAPbI3 material, however, remain at the forefront of current research. Due to the toxicity of lead and a purely fundamental interest in dicationic organic groups in place of monocationic MA+, less toxic dicationic bismuth–halide materials are the object of my research. The bismuth–iodide networks of the materials under investigation were hypothesized to form chains that extend in one dimension, whereas in MAPbI3 the lead–iodide network forms a lattice in three dimensions. If a small dicationic organic group is incorporated into the structure, however, it was hypothesized that the bismuth–iodide chains are in close enough proximity to each other to provide for long-range charge transport in three dimensions, similar to that observed in MAPbI3. A library of dicationic bismuth–halide materials has been investigated to determine optimal dicationic groups based on film quality, optical band gap, and current density versus potential (J–E) characteristics. XRD data of dicationic bismuth–halide thin films have suggested larger average crystal grain size than MAPbI3 thin films and SEM images of dicationic bismuth–halide thin films have indicated greater surface coverage than MAPbI3 thin films. UV–Vis absorption spectra of dicationic bismuth–halide thin films have revealed onsets of light absorption in the range of 565 nm to 620 nm, which correspond to optical band gaps between 2.2 and 2.0 eV. J–E measurements have indicated that dicationic bismuth–halide photovoltaic devices exhibit a photovoltage of almost 400 mV (Fig. 1). Thermal stability tests suggest that dicationic bismuth–halide thin films are significantly more robust than MAPbI3 thin films. Large single crystals have been obtained for a dicationic bismuth–halide material, and single-crystal XRD data have indicated that the material formed binuclear clusters of Bi2I10 4-, with two dicationic organic groups and two H2O molecules associated with each binuclear cluster. To my knowledge, this represents the first report of a crystal structure of this material. Efficient photovoltaic devices featuring a dicationic bismuth–halide material may offer a more environmentally friendly, stable alternative to MAPbI3 photovoltaic devices that currently dominate emerging photovoltaic technology research. Figure 1

Crystal structure of a new hybrid compound based on an iodido-plumbate(II) anionic motif.

Crystals of the one-dimensional organic-inorganic lead iodide-based compound catena-poly[bis-(piperazine-1,4-diium) [[tetra-iodido-plumbate(II)]-μ-iodido] iodide monohydrate], (C4N2H12)2[PbI5]I·H2O, were obtained by slow evaporation at room temperature of a solution containing lead iodide and piperazine in a 1:2 molar ratio. Inorganic lead iodide chains, organic (C4N2H12)(2+) cations, water mol-ecules of crystallization and isolated I(-) anions are connected through N-H⋯·I, N-H⋯OW and OW-H⋯I hydrogen-bond inter-actions. Zigzag chains of corner-sharing [PbI6](4-) octa-hedra with composition [PbI4/1I2/2](3-) running parallel to the a axis are present in the structure packing.

A 2D silver-iodide-organic framework with both fluorescent and phosphorescent emissions

Abstract Treatment of bix (1, 4-bis(imidazole-1-ylmethyl)benzene) with AgI generated [(Ag4I4)(bix)]n 1, whose crystal structure reveals a 2D organic–inorganic layer formed by novel wave-like silver(I) iodide chains with the linkers of bix ligands. The layers are arranged in parallel with the mode of {ABAB…} type showing 1D rectangular channels. In solid state, 1 exhibits multiple emission properties originating from its different natures, while optical absorption spectrum suggests that 1 might be a potential wide-gap semiconductor.

Photoconductivity induced by wire-to-spacer charge-transfer transitions in an inorganic-organic hybrid quasi-one-dimensional crystal: Polaron excitation in the Urbach tail

Photocurrent excitation spectra have been measured as a function of applied electric field and temperature with crystals of an inorganic-organic hybrid quasi-one-dimensional compound, methylviologen lead iodide, which consists of lead iodide chains and methylviologen spacer molecules. Photocurrent is induced dominantly by charge-transfer transitions from the lead iodide chains to methylviologen in the energy region between 2.1 and $\ensuremath{\sim}2.7\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$. Furthermore, the photoconductivity parallel to the inorganic chains is enhanced remarkably in the low-energy absorption tail of the charge-transfer transition, but not for the perpendicular current direction. It is revealed that the photocurrent enhancement is associated with the excitation in the Urbach tail of the charge transfer transition, which gives rise to electrons localized on methylviologen and hole polarons in the lead iodide chains. The photoconductivity enhancement is discussed and explained by the one-dimensional transport of photocreated hole polarons.

Charge-transfer transitions between wires and spacers in an inorganic-organic quasi-one-dimensional crystal methylviologen lead iodide

We have studied the optical property and electronic structure of an inorganic-organic quasi-one-dimensional crystal, methylviologen lead iodide. Two absorption bands were observed in the near ultraviolet and visible regions. The one is an absorption band at $3.1\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$ with a large oscillator strength, which is assigned to one-dimensional excitons confined in the inorganic chains. The other is a broad band observed between 2.0 and $2.8\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$ and attributed to charge-transfer transitions from the lead iodide chains to the methylviologen molecules. From the luminescence excitation spectra, it is found that there are two kinds of charge-transfer transitions from the valence band and the nonbonding state of the inorganic chains to the lowest unoccupied molecular orbital of methylviologen.

Layered organic-based metal iodide-polyiodide with unique mixed-valent gold(I/III) iodide chains.

We report the synthesis, optical spectrum, and crystal and electronic structures of a new organic-inorganic hybrid compound, [(p-NH3C6H4)2CH2]4 [(AuI2)(AuI4)(I2)2(I5)2Cl4], with unique mixed-valent gold(I/III) chains. The chains feature face-shared octahedral [AuIAu(III)I6]2- units and are embedded within polyiodide layers. The new mixed-valent gold iodide crystallizes in the orthorhombic space group Pnnm, with a = 27.0703(2), b = 8.9363(5), c = 18.4280(1) angstroms, Z = 2, and exhibits an optical band gap of 0.53 eV.

A copper(I) iodide chain with the 2-amino-4,6-dimethylpyridine cation

In the title compound, (2-amino-4,6-di­methyl­pyridinium) ­di­iodo­cuprate(I), (C7H11N2)[CuI2], the planar 2-amino-4,6-di­methyl­pyridine species is protonated at the pyridine N atom. It interacts with the inorganic chains by extensive hydrogen bonding. The cation forms N—H⋯I hydrogen bonds from both its pyridine and amine N atoms. The copper(I) species is tetrahedrally bonded to four iodide ions (average Cu—I distance = 2.665 A, with a standard uncertainty of 0.019 A) and forms infinite edge-sharing chains. Atom-site symmetries: Cu (2); I, phenyl-C and N (m).

A New Luminescent Organic–Inorganic Hybrid Compound with Large Optical Nonlinearity

The successful incorporation of an organic chromophore with highly polarizable lead iodide chains in an organic–inorganic hybrid is revealed in this communication. The synthesis, structure, and preliminary studies of the linear and nonlinear optical (NLO) properties of the compound are divulged. The synergism exhibited between polarizable inorganic polymers and hyperpolarizable organic molecules provides a route to new multi-functional NLO materials.

Bonding considerations in metal iodide chain compounds: alkali metal scandium iondids (AxScI3) and metal iodides (MI3) (A = lithium, sodium; M = zirconium, niobium)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTBonding considerations in metal iodide chain compounds: alkali metal scandium iondids (AxScI3) and metal iodides (MI3) (A = lithium, sodium; M = zirconium, niobium)Peter K. Dorhout and John D. CorbettCite this: Inorg. Chem. 1991, 30, 17, 3326–3333Publication Date (Print):August 1, 1991Publication History Published online1 May 2002Published inissue 1 August 1991https://doi.org/10.1021/ic00017a020RIGHTS & PERMISSIONSArticle Views130Altmetric-Citations7LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (2 MB) Get e-Alerts Get e-Alerts