Polyiodide Salts Research Articles

Structure and in vitro antimicrobial activity of sulfamethoxazole and sulfadiazine polyiodide salts

Sulfamethoxazole (SMZ) and sulfadiazine (SDZ) drugs belong to class II or IV synthetic antibiotics, which require higher doses for oral-administered formulations. Since, the multiplication and multi-factorial drug formulations are interesting tool to overcome such limitations, two poly-iodide salts of those two drugs, namely, SMZ[I5].H2O and SDZ2[I4] are presented herein. The systematic characterizations by powder X-ray diffraction, Fourier transform infrared, ultraviolet/visible spectroscopy, differential thermal analysis, thermogravimetry and single X-ray crystal structures of the SMZ[I5].H2O and SDZ2[I4] are presented. Sulfonamidepolyiodide salts were tested in vitro against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Candida tropicalis, Candida krusei, and Candida albicans to show the enhanced antimicrobial activity of the SMZ[I5].H2O in comparison with unmodified sulfonamide (SMZ).

Isolation of unique heterocycles formed from pyridine-thiocarboxamides as diiodine, iodide, or polyiodide salts

The reaction of pyridine-thiocarboxamides with I2 provided a variety of novel heterocyclic products as iodide, triiodide, and/or pentaiodide salts. Bismuth triiodide was incorporated as a crystallization aid to access other structural types.

Synthesis and Iodometric Analysis of the Polyiodide Salt (NMe4)[I5

This paper describes a first-year undergraduate exercise involving the synthesis of an “unknown” polyiodide salt, (NMe4)[I5], and the determination of its formula using the classic iodine–thiosulfate (iodometric) titration. The exercise introduces students to simple synthetic and titrimetric techniques, assists the development of their chemical and glassware handling and titrimetric skills, and acquaints them with unfamiliar polyiodide compounds. It also introduces students to key chemical concepts such as The Law of Definite Proportions, percentage elemental composition, empirical chemical formulas, quantitative stoichiometric reactions, and halogen catenation.

Pressure-Induced Polymerization and Electrical Conductivity of a Polyiodide.

We report the high-pressure structural characterization of an organic polyiodide salt in which a progressive addition of iodine to triiodide groups occurs. Compression leads to the initial formation of discrete heptaiodide units, followed by polymerization to a 3D anionic network. Although the structural changes appear to be continuous, the insulating salt becomes a semiconducting polymer above 10 GPa. The features of the pre-reactive state and the polymerized state are revealed by analysis of the computed electron and energy densities. The unusually high electrical conductivity can be explained with the formation of new bonds.

Pressure‐Induced Polymerization and Electrical Conductivity of a Polyiodide

AbstractWe report the high‐pressure structural characterization of an organic polyiodide salt in which a progressive addition of iodine to triiodide groups occurs. Compression leads to the initial formation of discrete heptaiodide units, followed by polymerization to a 3D anionic network. Although the structural changes appear to be continuous, the insulating salt becomes a semiconducting polymer above 10 GPa. The features of the pre‐reactive state and the polymerized state are revealed by analysis of the computed electron and energy densities. The unusually high electrical conductivity can be explained with the formation of new bonds.

Synthesis, crystal structure and Hirshfeld analysis of a new crystalline modification of the radical ion salt octa-methyl-ene-tetra-thia-fulvalenium triiodide (OMTTF)I3.

The reaction between 4,5,6,7-tetra-hydro-2-(4,5,6,7-tetra-hydro-1,3-benzodi-thiol-2-yl-idene)-1,3-benzodi-thiole (common name: 4,4',5,5',6,6',7,7'-octa-hydro-dibenzo-tetra-thia-fulvalene, OMTTF) and an excess of iodine in tetra-hydro-furan (THF) yielded the respective radical organic polyiodide salt, C14H16S4 +·I3 -. The asymmetric unit contains one and a half formula unit of both the cation and the anion, with the half-ions completed through inversion symmetry. The (OMTTF +) positive charge can be assigned by the bond distances and the planar structure of the C2S2C=CS2C2 central fragment. In the crystal, trimers of triiodide anions are connected through secondary inter-molecular I⋯I inter-actions into almost linear I9 3- polyanions. The non-centrosymmetric OMTTF radical cations are linked by S⋯S inter-actions into centrosymmetric dimers, while the centrosymmetric OMTTF cations remain as discrete units. The (OMTTF +) radical cations and the triiodide anions are linked by weak C-H⋯I and C-H⋯S inter-actions into a three-dimensional network. This work reports the fourth crystalline modification of the C14H16S4 +·I3 - salt. The three previous modifications were obtained from a mixture of aceto-nitrile and toluene [Konarev et al. (2005 ▸). Synth. Met. 151, 231-238].

Iodine/Iodide-Free Dye-Sensitized Solar Cells

Dye-sensitized solar cells (DSSCs) are built from nanocrystalline anatase TiO(2) with a 101 crystal face (nc-TiO(2)) onto which a dye is absorbed, ruthenium complex sensitizers, fluid I(-)/I(3)(-) redox couples with electrolytes, and a Pt-coated counter electrode. DSSCs have now reached efficiencies as high as 11%, and G24 Innovation (Cardiff, U.K.) is currently manufacturing them for commercial use. These devices offer several distinct advantages. On the basis of the electron lifetime and diffusion coefficient in the nc-TiO(2) layer, DSSCs maintain a diffusion length on the order of several micrometers when the dyed-nc-TiO(2) porous layer is covered by redox electrolytes of lithium and/or imidazolium iodide and their polyiodide salts. The fluid iodide/iodine (I(-)/I(3)(-)) redox electrolytes can infiltrate deep inside the intertwined nc-TiO(2) layers, promoting the mobility of the nc-TiO(2) layers and serving as a hole-transport material of DSSCs. As a result, these materials eventually give a respectable photovoltaic performance. On the other hand, fluid I(-)/I(3)(-) redox shuttles have certain disadvantages: reduced performance control and long-term stability and incompatibility with some metallic component materials. The I(-)/I(3)(-) redox shuttle shows a significant loss in short circuit current density and a slight loss in open circuit voltage, particularly in highly viscous electrolyte-based DSSC systems. Iodine can also act as an oxidizing agent, corroding metals, such as the grid metal Ag and the Pt mediator on the cathode, especially in the presence of water and oxygen. In addition, the electrolytes (I(-)/I(3)(-)) can absorb visible light (lambda = approximately 430 nm), leading to photocurrent loss in the DSSC. Therefore, the introduction of iodide/iodine-free electrolytes or hole-transport materials (HTMs) could lead to cost-effective alternatives to TiO(2) DSSCs. In this Account, we discuss the iodide/iodine-free redox couple as a substitute for the fluid I(-)/I(3)(-) redox shuttle. We also review the adaptation of solid-state HTMs to the iodide/iodine-free solid-state DSSCs with an emphasis on their pore filling and charge mobility in devices and the relationship of those values to the performance of the resulting iodide/iodine-free DSSCs. We demonstrate how the structures of the sensitizing dye molecules and additives of lithium or imidazolium salts influence device performance. In addition, the self-organizing molecular interaction for electronic contact of HTMs to dye molecules plays an important role in unidirectional charge diffusion at interfaces. The poly(3,4-ethylenedioxythiophene) (PEDOT)-based DSSCs, which we obtain through photoelectrochemical polymerization (PEP) using 3-alkylthiophen-bearing ruthenium dye, HRS-1, and bis-EDOT, demonstrates the importance of nonbonding interface contact (e.g., pi-pi-stacking) for the successful inclusion of HTMs.

Extended structures of polyiodide salts of transition metal macrocyclic complexes

The structures of five polyiodide salts, [Co([9]aneS3)2]I11 (1), [Ni([9]aneS3)2]I6 (2), [Ni([9]aneS3)2]I10 (3), [Pd([12]aneS4)]I6 (4) and [Pd([14]aneS4)]I10.MeCN (5), containing the template cations [Co([9]aneS3)2]3+, [Ni([9]aneS3)2]2+, [Pd([12]aneS4)]2+ and [Pd([14]aneS4)]2+ ([9]aneS3=1,4,7-trithiacyclononane, [12]aneS4=1,4,7,10-tetrathiacyclododecane, [14]aneS4=1,4,8,11-tetrathiacyclotetradecane) exhibit a range of polyiodide and polyanionic framework structures. In (1) the charge on the CoIII cation is balanced by three I3- anions, which along with a neutral di-iodine molecule form I(11)3- rings in an extended structure comprising undulating chains of alternating I11(3-) rings and complex cations. In (2) the complex cation is linked to two tri-iodide anions by S...I interactions into well separated sheets of cations and anions, while in (3), I5- anions are linked by I...I interactions into helices which are cross-linked by S...I contacts to form sheets. Rather longer I...I contacts in (4) assemble I3- ions into 2x2 rods, which are linked into a three-dimensional network by S...I contacts. In (5) the N atom of the acetonitrile solvent molecule forms an array of four weak C-H...N hydrogen bonds to the macrocycle. The extended structure comprises corrugated zigzag chains of polyiodide rings formed by linked I_5;- units; the complex cations are attached to the polyiodide network by S...I contacts, which link the chains to form layers.

Syntheses and structures of two acridine orange polyiodide salts

Polyiodide salts of acridine orange were isolated from solutions of an acridine and I2 in methylene chloride, ethanol, and acetone. The products from all solutions were found to contain both amorphous and crystalline material. The isolated crystalline product from methylene chloride and ethanol were identical (1), but the product isolated from acetone was different (2). Complex 1 was formulated as [C17H19N3(H)]2(I)2ċ 3I2. It crystallizes in the monoclinic space group P21/n, with a = 9.082(2) A, b = 24.027(4) A, c = 10.683(1) A, β = 107.20(1)○, and D(calc) = 2.31 Mg/m3. Complex 2 was formulated as [C17H19N3(H)]I3. It crystallizes in the triclinic space group P − 1, with a = 10.498(2) A, b = 11.265(2) A, c = 9.287(1) A, αg 100.88(1)○, β = 94.57(1)○, γ = 102.10(1)○, and D(calc) = 2.05 Mg/m3.

The reaction of iodine with 9-methylacridine: formation of polyiodide salts and a charge-transfer complex

The reaction of iodine and 9-methylacridine in methylene chloride results not in the formation of a charge-transfer complex as with acridine, but in the iodine-rich salt [ICH2C13H8N–H]4(I8)(I5)2, 8, where a proton on the methyl group has been replaced by an iodine. In toluene, the reaction produces both a charge-transfer complex ICH2C13H8N–I2, 9, and a salt [CH3–acridine(H)]2(I7)(I5), 10. Polyiodide salt formation can be explained by the availability of a facile reaction pathway from the aryl radical cation which results from initial oxidation by I2.

Conducteurs organiques: Preparation et Caracterisation de Sels a Transfert de Charge de bis(selenopyrannylidenes)-4:4’ Avec L'iode

Abstract Radical cation salts of 2,2′,6,6′-tetra(methyl and aryl)-4,4′-biselenopyranylidenes, are prepared by direct iodine oxidation. Several polyiodide salts are isolated (from each donor), the stoichiometries of which are a function of molecular ratio of the reagents. The salts are investigated by optical absorption spectroscopy (between 0.025 and 4.94 eV) and conductivity measurement determined on compressed pellets at room temperature. Optical spectra show peculiar absorption peaks: above 1 eV, intramolecular and isovalent transition peaks and between 0.25 and 0.99 eV, for the complexes with low iodine stoichiometry, and intervalence charge-transfer transition band relative to a transition between neutral donor and radical-cation. This band is characteristic of a mixed valence state. The degree of charge-transfer increases when the iodine stoichiometry increases for a given substituent with a subsequent decrease of the electrical conductivity attributed to an augmentation of the Coulomb's repulsions. Three mixed-valence polyiodides salts of the 2,2′,6,6′-tetraphenyl-4,4′-biselenopyranylidine: (1:2), (1:3.5) and (1:5.9), have been characterized further. The resonance Raman spectra display two kinds of iodine species, I − 3 and I − 5, in the 1:3.5 and 1:5.9 salts. The structure of the 1:2 salt has been investigated by X-ray diffraction. A compact, regular and segregated structure of the donor molecules along the axis is identified. The donor stacks delimit channels filled with linear polyiodide chains. This confirms the observed stoichiometry and results in a charge-transfer of 0.67 electron per donor for the 1:2 salt (2b-(I- 3)0,67). The (1:3.5) complex has a semiconducting behavior from 115 to 255 K and a single-crystal electrical conductivity of 4 S.cm−1 at room temperature. This semiconducting state and that of the 1:5.9 salt are derived from the reflectance spectra (performed on polycrystalline compaction) between 0.12 and 1.23 eV where the reflectivity decreases towards the infrared. On the contrary, the 1:2 salt shows a reflectance value about 25% from the infra-red (0.12 eV) to the Drude edge (0.41 eV) consistent with a quasione dimensional metallic character. The Drude's model affords an optical conductivity of 541 S.cm−1. This metallic state is also revealed in a weak variation of the 1:2 salt static paramagnetic susceptibility with temperature. This temperature dependence increases with iodine content and matches a Curie-Weiss behaviour for the 1:5.9 salt, whose stoichiometry deduced from the susceptibility study is (2b-(I- 3)0,67).

The crystal structures of two polyiodide salts of organic cations

The crystal structures of two polyiodide salts of organic cations

ChemInform Abstract: CRYSTAL STRUCTURES OF POLYIODIDE SALTS AND MOLECULAR COMPLEXES. 7. INTERACTION OF THIONES WITH MOLECULAR DIIODINE. THE CRYSTAL STRUCTURES OF DITHIZONE‐DIIODINE, ETHYLENETHIOUREA‐BIS(DIIODINE), BIS(ETHYLENETHIOUREA)‐TRIS(DIIODINE), BIS(DITHIZONE)‐HEPTAKIS(DIIODINE), AND 1‐(1‐IMIDAZOLIN‐2‐YL)‐2‐THIOXOIMIDAZOLIDINIUM TRIIODIDE‐(ETHYLENETHIOUREA‐DIIODINE)

Chemischer InformationsdienstVolume 15, Issue 31 Physical Organic Chemistry ChemInform Abstract: CRYSTAL STRUCTURES OF POLYIODIDE SALTS AND MOLECULAR COMPLEXES. 7. INTERACTION OF THIONES WITH MOLECULAR DIIODINE. THE CRYSTAL STRUCTURES OF DITHIZONE-DIIODINE, ETHYLENETHIOUREA-BIS(DIIODINE), BIS(ETHYLENETHIOUREA)-TRIS(DIIODINE), BIS(DITHIZONE)-HEPTAKIS(DIIODINE), AND 1-(1-IMIDAZOLIN-2-YL)-2-THIOXOIMIDAZOLIDINIUM TRIIODIDE-(ETHYLENETHIOUREA-DIIODINE) F. H. HERBSTEIN, F. H. HERBSTEINSearch for more papers by this authorW. SCHWOTZER, W. SCHWOTZERSearch for more papers by this author F. H. HERBSTEIN, F. H. HERBSTEINSearch for more papers by this authorW. SCHWOTZER, W. SCHWOTZERSearch for more papers by this author First published: July 31, 1984 https://doi.org/10.1002/chin.198431064AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume15, Issue31July 31, 1984 RelatedInformation

Performance of Ag/RbAg4I5/I2 solid electrolyte batteries after ten years storage

Solid state batteries were designed around the high conductivity solid electrolyte material RbAg4I5, with the polyiodide salts of tetramethylammnium iodide (Me4NI5 and Me4NI9) as cathodes and silver as the anode. Three-volt batteries, comprising five cells were designed into a hermetic package and fabricated for evaluaton. In March of 1983 these batteries completed 10 years of sto rage at temperatures of -15°C and 23°C. Some disproportionation of the solid electrolyte occurred during the low temperature storage with an increase in the resistance of about two orders of magnitude. This resistive degradation of the batteries was found to be reversible.

ChemInform Abstract: CRYSTAL STRUCTURES OF POLYIODIDE SALTS AND MOLECULAR COMPLEXES. PART VI. CRYSTAL STRUCTURE OF TETRAKIS(PHENACETIN) DIHYDROGENTETRAIODIDE DIHYDRATE ((H5C2OC6H4N(H)C(CH3):O)4.H2I4.2H2O)

Chemischer InformationsdienstVolume 14, Issue 17 Physical Organic Chemistry ChemInform Abstract: CRYSTAL STRUCTURES OF POLYIODIDE SALTS AND MOLECULAR COMPLEXES. PART VI. CRYSTAL STRUCTURE OF TETRAKIS(PHENACETIN) DIHYDROGENTETRAIODIDE DIHYDRATE ((H5C2OC6H4N(H)C(CH3):O)4.H2I4.2H2O) F. H. HERBSTEIN, F. H. HERBSTEINSearch for more papers by this authorM. KAPON, M. KAPONSearch for more papers by this authorW. SCHWOTZER, W. SCHWOTZERSearch for more papers by this author F. H. HERBSTEIN, F. H. HERBSTEINSearch for more papers by this authorM. KAPON, M. KAPONSearch for more papers by this authorW. SCHWOTZER, W. SCHWOTZERSearch for more papers by this author First published: April 26, 1983 https://doi.org/10.1002/chin.198317075Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume14, Issue17April 26, 1983 RelatedInformation

Mixed valence polyiodides from tetraphenyldithiapyranylidene: Crystalline structure and optical properties

Two conducting polyiodide salts have been obtained by direct oxidation of the donor DIPSØ 4 by iodine. These salts are characterized by X-ray diffraction, Raman and optical spectroscopy. The nature of iodine species is determined and the degree of charge transfer is evaluated.

The crystal structures of the polyiodide salts (phenacetin) 2 HI 5 and (theobromine) 2 H 2 I 8

The crystal structures of (phenacetin) 2 • H I 5 (triclinic, a — 12.44 A, b — 10.67, c = 5.81, oc = 103.3°, B — 103.7, y — 87.3, P1, Z = 1) and (theobromine) 2 H 2 I 8 (triclinic, a — 14.38 A, b = 14.07, c = 7.75, = 91.2°, B = 100.8, y = 91.0, P1, Z = 2) have been solved by Patterson methods, using intensities measured by Weissenberg diffractometer with graphite-monochromated Mo Ka radiation (2815 and 2827 intensities, R = 8.3 % and 11.1 % respectively). Both structures are polyiodide salts, with alternating cationic (organic) and anionic (polyiodide) layers. In (phenacetin) 2 • H I 5 the organic layers consist of hydrogen-bonded phenacetin 'dimers', with the proton bridging the oxygens of the carbonyl bonds in a short hydrogen bond ( d (O ...O ) = 2.46 (2) A); the polyiodide layers contain zigzag chains of alternating iodine molecules and triiodide ions, with secondary bonds ( d (I...I) = 3.55 A) between these moieties. There is only van der Waals bonding between parallel chains. This substance, bis- (phenacetin) hydrogen iodine triiodide, is a type A basic salt. In (theobromine) 2 • H 2 I 8 the organic layer consists of hydrogen-bonded theobrominium cations and the polyiodide layer of centrosymmetric S-shaped (I 4-16 ) ions, with the arrangement I - 3 •I - 2 •I - 3 •I - 3 •I - 2 •I - 3 ; there is secondary bonding between triiodide and iodine moieties within the hexadecaiodide ions. There are tertiary bonds (d/(I...I) = 3.84 A) between adjacent I 4-16 ions.

I16 4? Ions in crystalline (theobromine)2.H2I8; X-ray structure of (theobromine)2.H2I8

Crystal structure analysis shows that (theobromine)2.H2I8 is a polyiodide salt composed of alternating cationic and anionic layers; the former consist of hydrogen-bonded protonated theobromine species and the latter of I164– polyiodide ions.