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A three‐component reaction involving alkenes, N‐sulfonylhydrazones, and N‐bromosuccinimide (NBS) is described that uses Indium(III) triflate for the synthesis of bromoethyl sulfonyl hydrazones. Using N‐tosylhydrazones as a nitrogen source and NBS as a bromine source, this intermolecular aminobromination of alkenes is carried out under air in mild conditions. A mechanism of electrophilic addition is proposed based on the GC‐MS analytical result. [ABSTRACT FROM AUTHOR]

The aim of this work is to explore a new library of coordination compounds for medicinal applications. Gallium is known for its various applications in this field. Presently, indium is not particularly important in medicine, but it shares a lot of chemical traits with its above-mentioned lighter companion, gallium, and is also used in radio imaging. These metals are combined with thiosemicarbazones, ligating compounds increasingly known for their biological and pharmaceutical applications. In particular, the few ligands chosen to interact with these hard metal ions share the ideal affinity for a high charge density. Therefore, in this work we describe the synthesis and the characterization of the resulting coordination compounds. The yields of the reactions vary from a minimum of 21% to a maximum of 82%, using a fast and easy procedure. Nuclear Magnetic Resonance (NMR) and Infra Red (IR) spectroscopy, mass spectrometry, elemental analysis, and X-ray Diffraction (XRD) confirm the formation of stable compounds in all cases and a ligand-to-metal 2:1 stoichiometry with both cations. In addition, we further investigated their chemical and biological characteristics, via UV-visible titrations, stability tests, and cytotoxicity and antibiotic assays. The results confirm a strong stability in all explored conditions, which suggests that these compounds are more suitable for radio imaging applications rather than for antitumoral or antimicrobic ones. [ABSTRACT FROM AUTHOR]

A novel method for extracting and measuring trace amounts of indium, gallium, and thallium using a synthesized [2]rotaxane hydroxamic acid is proposed. The method involves extracting the elements at specific pH levels using chloroform and measuring them using spectrophotometry and inductively couples plasma atomic emission spectrometry (ICP-AES). The extraction mechanism and the factors that influence the extraction process are also discussed. The method is shown to be effective for measuring these elements in a variety of samples, such as alloys, environmental samples, minerals, water, and biological samples. The sensitivity of this method is enhanced 60 times by ICP-AES measurements, which makes it useful for trace determination of In, Ga, and Tl. [ABSTRACT FROM AUTHOR]

Compared with the traditional liquid–liquid extraction method, solid-phase extraction agents are of great significance for the recovery of indium metal due to their convenience, free of organic solvents, and fully exposed activity. In this study, P 2 O 4 (di-2-ethylhexyl phosphoric acid) was chemically modified by using UiO-66 to form the solid-phase extraction agent P 2 O 4 -UiO-66-MOFs (di-2-ethylhexyl phosphoric acid-UiO-66-metal-organic frameworks) to adsorb In(III). The results show that the Zr of UiO-66 bonds with the P-OH of P 2 O 4 to form a composite P 2 O 4 -UiO-66-MOF, which was confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). The adsorption process of indium on P 2 O 4 -UiO-66-MOFs followed pseudo first-order kinetics, and the adsorption isotherms fit the Langmuir adsorption isotherm model. The adsorption capabilities can reach 192.8 mg/g. After five consecutive cycles of adsorption-desorption-regeneration, the indium adsorption capacity by P 2 O 4 -UiO-66-MOFs remained above 99%. The adsorption mechanism analysis showed that the P=O and P-OH of P 2 O 4 molecules coated on the surface of P 2 O 4 -UiO-66-MOFs participated in the adsorption reaction of indium. In this paper, the extractant P 2 O 4 was modified into solid P 2 O 4 -UiO-66-MOFs for the first time. This work provides a new idea for the development of solid-phase extractants for the recovery of indium. [Display omitted] [ABSTRACT FROM AUTHOR]

A robust heterometal-organic framework with [In 2 Cd(OH)(O 2 CR) 5 (H 2 O) 5 ] cluster as secondary building unit displays excellent catalytic activity on the chemical fixation of CO 2 and Knoevenagel condensation. [Display omitted] • NUC- 103 is a heterometallic {In 2 CdO}-organic framework with scarcely reported [In 2 Cd(OH)(O 2 CR) 5 (H 2 O) 5 ] clusters as modes. • In NUC-103 , three rows of {In 2 CdO} are shaped into hierarchical nanochannels of 17.42 × 17.98 Å2 and 10.15 × 11.00 Å2. • NUC-103a displays the excellent catalytic performance on the cycloaddition of CO 2 with epoxides under mild conditions. The catalytic performance of MOFs mainly comes from the coordination defects of their metal ions. However, developing promising MOF catalysts with a large number of small coordination molecules on metal ions remains a huge challenge. Herein, we report a highly robust heterometallic {In 2 CdO}-organic framework of {[In 2 Cd(CPPDP)(µ 3 − OH)(H 2 O) 5 ](NO 3) 2 ⋅2DMF⋅3H 2 O} n (NUC-103) with scarcely reported [In 2 Cd(OH)(O 2 CR) 5 (H 2 O) 5 ] clusters (abbreviated as {In 2 CdO}) as secondary building units (SBUs), each of which contains five associated water molecules, implying that activated host framework can serve as strong Lewis acid. In NUC-103 , three rows of {In 2 CdO} are shaped into hierarchical triangle-nanochannels of 17.42 × 17.98 Å2 and triangle-microchannels of 10.15 × 11.00 Å2 along c axis. On account of the following unique characteristics such as three kinds of active sites (Lewis acid sites of In3+ and Cd2+, Lewis base sites of free N pyridine atoms and electrophilic H-bond donors (HBD) of µ 3 − OH moieties), large solvent-free channels, high thermal stability, and resistance to various solvents, NUC-103a is a promising catalytic platform. Catalytic experiments prove that NUC-103a is a significant heterogeneous catalyst for the cycloaddition of CO 2 with epoxides with exclusive selectivity and high conversion. In addition, NUC-103a as a bifunctional catalyst displays the high catalytic performance on the Knoevenagel condensation reactions of aldehydes and malononitrile. Therefore, this work not only provides an indium(III) + cadmium(II)-based heterometallic cluster of {In 2 CdO}, but also provides a valuable insight into designing metal–organic catalytic materials with high defect coordination. [ABSTRACT FROM AUTHOR]

A molecular aqua-fluoride complex of indium(III) InF 3 (H 2 O)(C 2 H 4 N 4) 2 (I) has been synthesized for the first time, along with its anhydrous analogue – InF 3 (C 2 H 4 N 4) 2 (II), which has been obtained by thermal dehydration of I. The crystal structure of I is formed by molecular complexes [InF 3 (H 2 O)(C 2 H 4 N 4) 2 ] linked through O–H⋯F and N–H⋯F hydrogen bonds. The structure of the compound II appeared to be chainlike; linear chains of the composition [ I N F 3 ( C 2 H 4 H 4 ) 2 ] 0 ∞ 1 are formed as a result of linking the isolated molecules of the complexes I by In–F–In bridge bonds, in which vacancies of the removed H 2 O molecules are occupied by F atoms of the neighboring molecules. The isolated chains are linked into a three-dimensional framework by N–H⋯F hydrogen bonds. In both compounds, In is coordinated by two neutral molecules of 4-amino-1,2,4-triazole. A distinctive feature of the InF 3 (H 2 O)(C 2 H 4 N 4) 2 compound is the presence of three different ligands in the coordination sphere of the indium atom: fluorine and, molecules of H 2 O and 4-amino-1,2,4-triazole.The thermal behavior and character of ionic motions have been investigated by means of thermogravimetry (TG, DTG, DTA), DSC and 19F,1H NMR spectroscopy. Structures of the InF 3 (H 2 O)(C 2 H 4 N 4) 2 , InF 3 (C 2 H 4 N 4) 2 , 1H NMR spectra of the InF 3 (H 2 O)(C 2 H 4 N 4) 2 at some temperatures. Image 1 • The first In(III) complex with 4-amino-1,2,4-triazole molecules InF 3 (H 2 O)(C 2 H 4 N 4) 2 (I) was synthesized. • A thermal study showed that the formation of InF 3 (C 2 H 4 N 4) 2 (II). • Structure I is formed from molecular complexes InF 3 (H 2 O)(C 2 H 4 N 4) 2. • Structure II is constructed from linear chains of compositions [InF 3 (C 2 H 4 N 4) 2 ]. • Analysis of NMR data allowed us to identify types of ion mobility in I and II compounds. [ABSTRACT FROM AUTHOR]

The simultaneous determination of Ga(III) and In(III) in environmental water samples was described. The procedure was based on adsorptive stripping voltammetry using an in situ plated bismuth film electrode as a working electrode. In order to obtain low detection limits and satisfactory separations of gallium and indium peaks on the voltammogram, cupferron was used as a complexing agent. The optimum composition of the supporting electrolyte was found to be: 0.1 mol l-1 acetate buffer (pH=5.0), 2 × 10-4 mol l-1 cupferron, 2 × 10-4 mol l-1 Bi(III), optimal voltammetric parameters were found to be: accumulation potential -0.9 V, accumulation time 60 s. The linear range of Ga(III) as well as In(III) was observed over a concentration range from 2.5 × 10-8 mol l-1 to 1.5 × 10-6 mol l-1. The method was satisfactorily applied to the simultaneous quantification of gallium and indium in environmental water samples. This facilitated a promising application of the recommended procedure for monitoring the environment, which is necessary to evaluate the soil-plant system. [ABSTRACT FROM AUTHOR]

Highlights • The ionic liquid is generated from the reaction between the amine and sulphuric acid solutions. • The extraction of indium(III) is heavily dependant of the acidity of the aqueous feed. • The system is not selective against the presence of Fe(III) or Sn(II) in the aqueous feed. • Indium(III) can be stripped with sulphuric acid solutions. Abstract The extraction of indium(III) from acidic sulphuric solution by the ionic liquid (PJMTH+HSO 4 −) was investigated. This ionic liquid was generated by reaction of the primary amine Primene JMT (PJMT) and sulphuric acid solutions. The metal extraction was investigated under various experimental conditions: equilibration time, temperature, metal and sulphuric acid concentrations in the aqueous feed and extractant concentration in the organic solution. Also, the selectivity of the present system against the presence of other metals in the aqueous feed was examined. Indium stripping is effectively done by the use of sulphuric acid solution. Extraction and stripping isotherms were generated within this work. [ABSTRACT FROM AUTHOR]

Crystal structures of CuInF5·7H2O and ZnGaF5·7H2O are determined. They are composed of centrosymmetric octahedral complex [Cu(1)(H2O)6]2+ and [Cu(2)(H2O)6]2+ ([Zn(1)(H2O)6]2+ and [Zn(2)(H2O)6]2+ respectively) cations and two types of centrosymmetric octahedral complex [In(1)F4(H2O)2]- and [In(2)F6]3- ([Ga(1)F4(H2O)2]- and [Ga(2)F6]3- respectively) anions. Coordinated H2O molecules in the complex [In(1)F4(H2O)2]- and [Ga(1)F4(H2O)2]- anions are in trans-positions. Branched systems of O-H...F and O-H...O hydrogen bonds organize the structural elements of the studied compounds into a three-dimensional framework. The unit cell parameters of some complex fluorides MIIAF5·7H2O (M = Co, Ni, Cu, Cd; A = In, Ga) are determined by X-ray diffraction of polycrystals and two isostructural series are identified. [ABSTRACT FROM AUTHOR]

Fluoride complexes of indium(III) with mixed monovalent M+ (M = Rb, Cs, NH4) and divalent [Cu(H2O)4]2+ cations of the composition M[Cu(H2O)4]InF6·nH2O (M = Rb, Cs, NH4; n = 0, 1) are synthesized for the first time and their crystal structures with a polymer chain character are studied. The structures of M[Cu(H2O)4]InF6·nH2O (M = Rb, Cs, NH4; n = 0, 1) are formed of monovalent Rb+, Cs+, NH4+ cations respectively, complex [Cu(H2O)4]2+ cations, slightly distorted octahedral complex [InF6]3- anions, and crystallization H2O molecules. By attaching one F atom from the neighboring InF6 groups, the [Cu(H2O)4]2+ cations form distorted octahedral Cu(H2O)4F2 groups. Via the bridging F atoms, the [Cu(H2O)4]2+ cations and [InF6]3- anions alternatively join into zigzag anionic polymer chains. A branched system of hydrogen O-H···F, O-H···Ow, and N-H···F bonds arrange the anionic chains into a threedimensional framework in whose voids the monovalent cations and crystallization H2O molecules are located. The structures of M[Cu(H2O)4]InF6·nH2O (M = Rb, Cs, NH4; n = 0, 1) are a new structure type. [ABSTRACT FROM AUTHOR]

A novel indium(III) ion imprinting polymer (IIP) for the selective separation of indium(III) ions from complex aqueous solution had been prepared by surface imprinting technique using vinylphosphonic acid and allyl mercaptan as the functional monomer and indium sulfate as a template. The adsorbent was characterized on the basis of infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TG) and energy dispersive X-ray spectrometer (EDX). The indium(III) ions adsorption behavior on the In(III)-IIP was investigated in detail by batch and column experiments. Sorption equilibrium was achieved within 30 min, the maximum static and dynamic adsorption capacities were 60.62 mg∙g −1 and 48.72 mg g −1 , respectively. The kinetic study indicated that the adsorption process could be better described by the pseudo-second-order model, and experimental data could be better fitted relied on the Langmuir adsorption isotherm model. The In(III)-IIP exhibited excellent selectivity for In(III) against the interfering ions, including K(I), Ca(II), Na(I), Mg(II), Mn(II), Cd(II), Ni(II), Co(II), Pb(II), Cu(II) and Zn(II) and the separation factors of IIP in the binary metal mixture solutions for In(III)/Cu(II), In(III)/Pb(II), In(III)/Zn(II) and In(III)/Fe(II) were calculated to be 41, 212, 37 and 69, respectively. After six adsorption-desorption cycles, no obvious loss in adsorption capacity was observed, indicating that the adsorbent had a high stability and reusability. Moreover, the In(III)-IIP was applied to the selective separation of indium(III) ions from the real wastewater with satisfactory results. [ABSTRACT FROM AUTHOR]

A new indium(III) fluoride complex Cu(InF)·10HO with the divalent Cu cation is synthesized for first time, and its crystal structure, which is a new type of the structure of complex fluorides of trivalent metals with divalent cations, obtained from a hydrofluoric acid solution, is studied. The structure of Cu(InF)·10HO is monoclinic, space group P2/a. The structure is formed by isolated centrosymmetric distorted octahedral complex [Cu(HO)] cations and isolated distorted octahedral complex [InF(HO)] anions with the cis arrangement of coordinated water molecules. The branched system of O-H·F hydrogen bonds, which is formed by the coordinated HO molecules with the F atoms of anions, combines the structural elements of the compound to form a three-dimensional framework. [ABSTRACT FROM AUTHOR]

The transport of indium(III) through pseudo-emulsion based hollow fiber strip dispersion technology was investigated. The extractant being an ionic liquid RNH 3 + HSO 4 − , previously generated from the reaction of the primary amine Primene JMT, dissolved in Solvesso 100, and sulphuric acid. The feed solution containing In(III) was flowed through the tube side, and pseudo-emulsion of RNH 3 + HSO 4 − /Solvesso 100 and sulphuric acid was passed through the shell side in counter-current mode, using a single fiber contactor for extraction and stripping. Several hydrodynamic and chemical parameters, such as variation in flows, feed pH (0.6–2), indium concentration in feed (0.01–0.1 g L −1 ), carrier concentration (0.0025–0.25 M), etc., were investigated. [ABSTRACT FROM AUTHOR]

The crystal structures of isostructural fluoride complexes of indium(III) M[InF(HO)] (M = Rb, Cs) crystallizing in the monoclinic system, space group I2/ a, are studied. The structures of M[InF(HO)] (M = Rb, Cs) are formed of isolated centrosymmetric complex [InF(HO)] anions with the trans-position of coordinated HO molecules and Rb, respectively Cs, cations. The In atom in the complex [InF(HO)] anion is surrounded by four F atoms and two oxygen atoms of coordinated HO molecules, forming the coordination polyhedron as a slightly distorted octahedron. Via a system of hydrogen O-H⋯F bonds the polyhedra of In atoms are arranged in a three-dimensional framework with the cations located in its channels. [ABSTRACT FROM AUTHOR]

The crystal structures of isostructural mixed-ligand fluorosulfate complex compounds of indium(III) M[InF(SO)HO] (M = K, NH), formed of K cations, NH respectively, and complex [InF(SO)HO] anions are determined. In the complex anion, the indium atom surrounded by three F atoms, the oxygen atom of the coordinated HO molecule, and two oxygen atoms of the bridging sulfate group forms a slightly distorted octahedron (CN 6). Via alternating bridging SO groups, the polyhedra of In(III) atoms are arranged in polymer chains. The O-H•••F hydrogen bonds organize the chains in a three-dimensional network. The K and NH cations are located in the structure framework and additionally strengthen it. [ABSTRACT FROM AUTHOR]

Isostructural fluorooxalate complex compounds of indium(III) M[InF(CO)HO] (M = K, Rb), being the first representatives of a new class of mixed-ligand fluoro-containing complex compounds of indium(III) are synthesized and structurally studied for the first time. The crystal structures of M[InF(CO)HO] (M = K, Rb) are formed of K cations (Rb respectively) and complex [InF(CO)HO] anions. The indium atom in the complex anion is surrounded by four F atoms, two of which are bridging, the oxygen atom of the coordinated HO molecule, and two oxygen atoms of the bis-bidentate (tetradentate) oxalate group. The coordination polyhedron of the indium atom (CN 7) is a pentagonal bipyramid. Via alternating double bridging F atoms and tetradentate bridging CO group, the In(III) atom polyhedra are arranged in polymers chains. Via hydrogen O-H⋯F bonds the chains are organized in layers. Between the layers, the K or Rb cations are located, which strengthen the crystal structure. [ABSTRACT FROM AUTHOR]

Two unusual indium–organic frameworks, InMOF- 1 and InMOF- 2 , have been successfully obtained by solvothermal reaction of trivalent indium ions and two flexible aromatic tetracarboxylate ligands. These compounds were characterized by single-crystal X-ray diffraction, IR spectroscopy, and powder X-ray diffraction (PXRD) measurement. In virtue of tetrahedral tri-positive and tetra-negative building blocks, their frameworks both exhibit anionic feature and are isomorphous in topology: twofold interpenetrating dia three-dimensional (3D) frameworks. Additionally, their solid-state photoluminescent properties have also been further investigated. [ABSTRACT FROM AUTHOR]

A total of 88 crystal lattice structures of indium(III) anionic fluoride and mixed-ligand fluoride complexes have been discussed and systematized. Most of these structures have been established by single-crystal X-ray diffraction techniques, but some were characterized by powder X-ray diffraction methods. The presented crystallography data were compared with known isotypical compounds. This paper offers a discussion of the geometry of indium and outer sphere cation coordination polyhedra; the association of indium atoms in dimer, oligomer, and polymer formations (chains, layers, frameworks); types of cation-anion interactions; and their contributions in actual three-dimensional crystal structures including types of the crystal lattices formed. We also used structural examples of potassium fluoroindates(III) to describe the basics of the structural depolymerization model for fluoride compounds, which is used to depict the formation and transformation of complex metal fluorides and predict structural types of novel or uncharacterized fluorides in the corresponding compound series. For the readers’ convenience, we have compiled structural information in a single table containing phase compositions and corresponding standard crystallographic data (such as crystal system, space group, unit cell parameters, number of formula units per cell [Z], reliability factors [R], and In-F and In-O bond lengths). [ABSTRACT FROM AUTHOR]

The work in this report deals with the syntheses, characterization and crystal structures of four compounds of composition [Ni II L OEt–pn (H 2 O) 2 Pb II Br 2 ] ( 1 ), [Ni II L OEt–pn (H 2 O) 2 Pb II (NO 3 ) 2 ] ( 2 ), [{Cu II L OEt–pn (μ-Br)Pb II } 2 (μ-Br) 2 ] ( 3 ) and [{Cu II (NO 3 )L OEt–pn In III (NO 3 )} 2 (μ-OH) 2 ] ( 4 ), where H 2 L OEt–pn is N , N ′-propanebis(3-ethoxysalicylaldimine). Copper(II)/nickel(II) in these compounds occupies the N(imine) 2 O(phenoxo) 2 compartment, while Pb II /In III occupies the O(phenoxo) 2 O(ethoxy) 2 compartment of the ligand. Compounds 1 and 2 are diphenoxo-bridged dinuclear, whereas two dinuclear units are dimerized in 3 and 4 . Copper(II) and indium(III) in the dinuclear unit in 4 are diphenoxo-bridged, while copper(II) and lead(II) in 3 are triply bridged by bis(μ-phenoxo)-μ-bromide moiety. Dimerization takes place by two bridging bromides (that bridge two Pb II centers) in 3 and by two bridging hydroxides (that bridge two In III centers) in 4 . Copper(II) in 3 and 4 are distorted square pyramidal, while nickel(II) centers in 1 and 2 are distorted octahedral. All the four oxygen atoms of the O(phenoxo) 2 O(ethoxy) 2 compartment are coordinated to the second metal ion (Pb II /In III ) in 1 – 4 . Coordination number of lead(II) is 6, 7 and 8 in 1 , 3 and 2 , respectively, while indium(III) in 4 is 8-coordinated. Salient features of the compounds are discussed. [ABSTRACT FROM AUTHOR]

A new indium(III) fluoride complex with the ammonium cation (NH)[InF] is synthesized and its crystal structure is studied. The structure of (NH)[InF] is formed of NH cations and complex [InF] anions. The In atom in the complex anion surrounded by four terminal and two bridging F atoms forms an almost regular octahedral coordination polyhedron (CN 6) with two terminal F atoms in the axial positions and two terminal and two bridging F atoms in the equatorial plane. Through bridging F atoms, the InF6 polyhedra are arranged in polymer trans- vertex-connected corrugated anion chains (InF) directed along the c axis. The N-H⋯F hydrogen bonds organize the chains in a three-dimensional framework. [ABSTRACT FROM AUTHOR]

The compatibility of indium(III) Lewis acids with water and amines allows their employment in synergistic and cooperative catalysis. Stereoselective organocatalytic SN1-type reactions, in which carbenium ions are generated, are promoted by the presence of indium salts. The peculiar properties of indium salts can be exploited in organocatalysis for the design of water-compatible, benign, green processes. The development of such indium(III)-promoted organocatalytic procedures is the focus of our recent re- search, a summary of which is presented in this article. [ABSTRACT FROM AUTHOR]

Abstract-To selectively adsorb indium(III) in industrial wastewater coexisting with zinc(II), the surface of sawdust was modified into phosphate groups through chemical reaction. Among various manufacturing methods, phosphorylated sawdsust made from using non-grinding sawdust with same ratio (based on volume) of HPO and distilled water had a very high selectivity to indium(III), which shows removal efficiency of about 90% with 1.0 g at pH 3.5. Meanwhile, in case of zinc(II), there is almost no adsorption onto phosphorylated sawdust. The surface condition and phosphorus content of phosphorylated sawdust were analyzed by scanning electron microscopy (SEM) photograph and energy dispersive x-ray (EDX) spectrum. Also, the effects of loading of adsorbent and time on selective adsorption characteristics of indium(III) were investigated. [ABSTRACT FROM AUTHOR]

The tris(dimethyldithioarsinato) complexes M(S2AsMe2)3 (M = Al, Ga, In and Tl) have been prepared from NaS2AsMe2·2H2O as anhydrous powders. The Al and Ga, but not the In and Tl, complexes add water molecules seen in the IR(KBr) spectra. The Al and Ga coordinate, while the In and Tl complexes attract and polarize water in CDCl3 resulting in more than one signal for H2O in the 1H NMR spectra. All four complexes are desulfurized by Ph3P but the expected M(SAsMe2)3 are unstable and decompose to Me2As-S-AsMe2 and other products. [ABSTRACT FROM AUTHOR]

Abstract: A modified solvent impregnated resin (MSIR) was prepared by impregnation of sec-octylphenoxy acetic acid (CA-12) on styrene–divinylbenzene copolymer support (HZ818) after nitration of the benzene rings present in its structure. The MSIRs were characterized by thermogravimetric and Fourier Transform infrared spectroscopy (FTIR) analysis. The adsorption behavior of indium(III) on MSIRs was examined by batch and column method in hydrochloric acid medium. It was shown that optimal pH for indium(III) adsorption was 3.0. The adsorption isotherms were found to follow Langmuir model at different temperatures, and the maximum adsorption capacity enhanced with increasing temperature. The value of enthalpy change was positive, indicating that the adsorption of indium(III) with MSIRs is endothermic. Kinetic data indicated that the adsorption of indium(III) was in a good agreement with the pseudo second-order rate equation. The MSIRs sustained adsorptivity well after three recycles comparing with the SIRs. [Copyright &y& Elsevier]

Abstract: Four indium(III)-biphenyl carboxylate coordination complexes: [In(dpdc)(bipy)Cl]2 (1), {[In(Hdptc)(bipy)]2·H2O} n (2), [In(dptc)·H3O] n (3), [In3(μ 2-OH)2(Hdptc)(dptc)H2O] n (4) (H2dpdc=diphenyl-2,2′-dicarboxylic acid, bipy=2,2′-bipyridine, H4dptc=biphenyl-2,2′,6,6′-tetracarboxylic acid) have been synthesized under hydrothermal and solvothermal conditions. Complex 1 exhibits a dimeric molecule structure featuring a square motif organized by two In(III) ions and two dpdc ligands each at the corner; 2 contains a similar dimeric segment which is extended into a 1D ribbon structure by the Hdptc ligands and further assembled into 2D supramolecular layer through hydrogen bonding; 3 features a 2D (4,4) grid layer, which is assembled into 3D supramolecular network through hydrogen bonding with guest water molecules. Complex 4 consists of an unprecedented eight-connected trinuclear In3(μ 2-O)2(CO2)8 building unit which is jointed by four-connected dptc ligand into a binodal (4,8)-connected scu topology. The results present a feasible way of manipulation to control the dimensionality of the complexes by adjusting ligands and reaction temperatures. The complexes are also characterized by X-ray powder diffractions (PXRD), infrared spectroscopy and elemental analysis. [Copyright &y& Elsevier]

Conditions have been established for the determination of Thallium(III) (Tl) and Indium(III) (In) individually and in mixtures. In the presence of sufficient chloride ions, Tl(III) forms the tetrachlorothallate(III), TlCl4 -, which forms a stable ion-pair association with the cationic part of methylene blue. Tl(III) is determined alone by direct titration with Ethylenediaminetetraacetic Acid (EDTA) using methylene blue as an ion-pair indicator. In(III) is titrated with EDTA in the presence of a known amount of Tl(III) and sufficient chloride with methylene blue as an ion-pair indicator. Moreover, direct titration of a mixture containing the two metal ions with EDTA results in successive complexation of the ions, first with In(III) and then with Tl(III). The equivalence point is reached in all cases when the pink color of the ion-pair association turns to blue. The titer value for the mixture corresponds to the total of In(III) and Tl(III) and a blank correction corresponding to Tl(III) is applied. In the analysis of the mixtures, the total amount of In(III) and Tl(III) is estimated complexometrically, while the Tl(III) alone is estimated bromatometrically after reducing to Tl(I). The amount of In(III) is calculated by difference. [ABSTRACT FROM AUTHOR]

Abstract: A synergistic extraction system consisting of sec-octylphenoxy acetic acid (CA12, H2A2) and primary amine N1923 (B) for gallium(III), indium(III), and zinc(II) has been developed from chloride medium. Synergistic and antagonistic effects are observed for the title metals at low and high CA12 concentration ratios, respectively. On the basis of the distribution ratios, the values of the separation factors are calculated and used for the discussion of the selectivities between gallium(III)/indium(III) and zinc(II). The synergistic extraction of zinc(II) with the mixtures has been investigated with the methods of slope analysis and constant mole. The synergistic adduct has been determined together with the equilibrium constant and thermodynamic constants. [Copyright &y& Elsevier]

Abstract: The structure of the N,N-dimethylthioformamide (DMTF) solvated gallium(III) ion has been determined in solution by means of extended X-ray absorption fine structure (EXAFS) spectroscopy. The gallium(III) ion is four-coordinate in tetrahedral fashion with a mean Ga–S bond distance of 2.233(2)Å in DMTF solution. At the dissolution of indium(III) perchlorate or trifluoromethanesulfonate in DMTF coordinated solvent molecules are partly reduced to sulfide ions, and a tetrameric complex with the composition [In4S4(SHN(CH3)2)12]4+ is formed. The structure of the solid tetrameric complex in the perchlorate salt was solved with single crystal X-ray diffraction. Four indium(III) ions and four sulfide ions form a highly symmetric heterocubane structure where each indium binds three bridging sulfide ions and each sulfide ion binds three indium(III) ions with a mean In–S bond distance of 2.584(1)Å, and S–In–S angles of 90.3(1)°. Each indium(III) additionally binds three DMTF molecules at significantly longer mean In–S bond distance, 2.703(1)Å; the S–In–S angles are in the range 80.3–90.4°. Large angle X-ray scattering data on a DMTF solution of indium(III) trifluoromethanesulfonate show that the same tetrameric species characterized in the solid state is also present in solution, whereas the EXAFS measurements only give information about the In–S bond distances due to the short core hole lifetime. [ABSTRACT FROM AUTHOR]

Abstract: The structures of the N,N′-dimethylpropyleneurea (DMPU) solvated gallium(III) and indium(III) ions have been determined in DMPU solution by means of EXAFS. The gallium(III) ion is five-coordinate with a mean Ga–O bond distance of 1.924(5)Å, while the larger indium(III) ion is octahedrally coordinated with a mean In–O bond distance of 2.146(3)Å. The complex formation equilibria in DMPU for the gallium(III) and indium(III) bromide systems have been studied calorimetrically at 298K. Three relatively strong complexes are formed in the indium(III) bromide system in DMPU, whereas no stability constants could be established in the gallium(III) bromide system as the heats of complex formation were very close to zero. Gallium(III) bromide is present as DMPU solvated GaBr3 complexes in solution with three equatorial Ga–Br bonds at 2.328(3)Å, and two Ga–O bonds at 1.92(3)Å in the apical positions of a distorted trigonal bipyramid. The DMPU solvated indium(III) bromide has the same configuration with a mean In–Br bond distance of 2.510(3)Å, and two In–O bonds at 2.201(6)Å. Indium(III) binds three bromides and three Me2SO molecules through the oxygen atoms in octahedral fac-configuration with mean In–Br and In–O bond distances of 2.630(3) and 2.211(15)Å, respectively. [Copyright &y& Elsevier]

A new solid-phase extraction method for separation and preconcentration of trace amounts of Ga(III) and In(III) in biological and water samples is proposed. The procedure is based on the adsorption of Ga(III) and In(III) ions on a column of Amberlite XAD-4 resin loaded with newly-synthesized pentadentate naphthol-derivative Schiff base 1-{[(6-{[(E)-1- (2-hydroxy-1-naphthyl)methylidene]amino}-2-pyridyl)imino]methyl}-2-naphthol (HMPN) prior to their determination by flame atomic absorption spectrometry (FAAS). The optimum pH values for quantitative sorption of Ga(III) and In(III) are 4.5-6.0 and 4.5-8.0, respectively, and their desorptions can be achieved by using 5 mL of 0.5 M HNO3. The sorption capacities of the resin for Ga(III) and In(III) were 1.27 and 1.45 mg g-1, respectively. The enrichment factor for preconcentration of Ga(III) and In(III) was found to be 200. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of ten replicates, was below 3% for both elements. The proposed procedure was applied to the analysis of synthetic seawater, natural waters, wastewater and human blood serum using flame AAS. [ABSTRACT FROM AUTHOR]

Abstract: A novel In(III) coordination complex, [In(ptc)(H2O)] n (H3ptc=4,4′,4″-phosphoryltribenzoic acid) (1), was synthesized under hydrothermal condition and characterized by single-crystal X-ray analysis, IR, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) and solid-state photoluminescence. Complex 1 crystallizes in a chiral P21 space group, In(III) ions are eight-coordinated and the ligand exhibits a novel and unique tetrahedral coordination mode. The complex shows intense blue emission at 435nm with the excitation of 330nm. [Copyright &y& Elsevier]

Abstract: Two novel In(III) complexes, [In(bna)(Hbna)] n (1) and [In2(bna)2(μ 2-OH)2] n ·4nH2O (2) (H2bna=2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylate acid), have been reported. Complex 1 adopts a 2D layer structure, where each layer composed from homochiral ligands is chiral while the ligands in two neighboring layers are enantiomer. Complex 2 is constructed by individual –In–O–In– chains, which are further connected by bna2− into a 3D honeycomb framework. As a derivative of H2bna ligand, dmbna (3) was recrystallized for structurally comparison with 1-2 (dmbna=dimethyl 2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylate). X-ray powder diffractions (XRD) and thermogravimetric analyses (TGA) for 1-2 show that they are highly thermally stable in the solid state. Complexes 1 and 2 exhibit the intense yellow luminescence at 573nm and blue luminescence at 459nm at room temperature, respectively. And an astonishing blue shift of 105nm is observed for complex 1 when it is measured at 10K. [Copyright &y& Elsevier]

A new chelating polymeric sorbent has been developed using impregnation of Amberlite XAD-7 resin with a newly-synthesized hexadentates naphthol-derivative Schiff base 1-[(1E,9E)-10-(2-hydroxy-1-naphthyl)-4,7-dioxa-2,9-diaza-1,9-decadienyl]-2-naphth (EHND). The impregnated resin showed high binding affinity for Ga(III) and In(III) ions and was used for their preconcentration prior to determination by flame AAS. The optimum pH values for the quantitative sorption of Ga(III) and In(III) are 4.0-6.0 and 4.5-8.0, respectively, and their desorptions can be achieved by using 5 mL of 1 M HNO3. The sorption capacities of the resin for gallium and indium were 1.1 and 1.3 mg g-1, respectively. The enrichment factor for preconcentration of gallium and indium was found to be 200. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of ten replicates, was below 2.5% for both elements. The practical applicability of the polymer was tested with synthetic seawater, natural waters, wastewater and human blood serum. [ABSTRACT FROM AUTHOR]

Extraction processes of indium(III) with 2-octylaminopyridine (2-OAP) from media of various complexing ability, succinate and salicylate, in chloroform have been elucidated. The ion-pair complex has also quantitative extraction in xylene and 1,2-dichloroethane. Indium(III) from organic phase was stripped with 1.0 M hydrochloric acid and determined complexometrically with EDTA. The stoichiometry of the extracted species was found out on the basis of slope analysis. The extraction of indium(III) proceeds by an anion exchange mechanism and the extracted species is [RR′NH2+In(succinate)2-](org). Temperature dependence of the extraction equilibrium constant was also examined to estimate the apparent thermodynamic functions (ΔH, ΔG and ΔS) for extraction reaction. It is possible to separate indium(III) from Zn(II), Cd(II), Pb(II), Hg(II), Bi(III), Tl(I), Tl(III), Ga(III), Al(III), Te(IV), Se(IV), Sb(III), Fe(III) and Sn(IV). The method is simple, rapid and reproducible and can be used to determine the indium from samples like alloys. [ABSTRACT FROM AUTHOR]

Abstract: The decomposition of the thiocyanate ion in acidic aqueous solution disturbs the complex formation reactions with gallium(III) and indium(III) to such an extent that any accurate stability constants cannot be obtained. Calorimetric studies have shown that several reactions besides the complex formation take place at the addition of thiocyanate to aqueous solutions of gallium(III) and indium(III). The origin of these reactions has not been possible to establish, but they seem to be metal ion dependent. An EXAFS study on an aqueous gallium(III) thiocyanate solution with excess thiocyanate showed the presence of hydrated gallium(III) ions and a small fraction of gallium(III) hydrolysis products at pH=2. This shows that the complex formation between gallium(III) and thiocyanate is very weak in aqueous solution if it takes place at all. The thiocyanate ion is stable in aprotic solvents as dimethylsulfoxide, and complex formation studies of gallium(III) and indium(III) with thiocyanate can be performed in a normal way. One weak mononuclear complex is formed in the gallium(III)- and indium(III)-thiocyanate systems in dimethylsulfoxide under prevailing conditions with K 1 and ΔH 1 values of 30±5 dm3 mol−1 and 9±2 kJ mol−1, and 105±9 dm3 mol−1 and 1.13±0.05 kJ mol−1, respectively. An EXAFS study on gallium(III) thiocyanate in dimethylsulfoxide solution showed that the thiocyanate ion is coordinated through the sulfur atom with a Ga–S bond distance of 2.198(6) Å, and a change in the coordination number of gallium(III) from six to five, with a mean Ga–O bond distance of 1.902(6) Å to the four dimethylsulfoxide molecules. [Copyright &y& Elsevier]

Abstract: The separation of In(III), Ga(III) and Zn(II) from sulfate solution has been studied using an extraction resin containing 2-ethylhexyl phosphoric acid mono(2-ethylhexyl) ester (P507 extraction resin). The effect of pH on the extraction of each metal was determined. Extraction isotherms were then constructed at selected pH. Results show that In(III) is first extracted from aqueous solutions at pH 2.0 using this resin while Ga(III) and Zn(II) are co-extracted at pH 3.0. Their separation can be carried out using HCl of different concentrations as eluants. The saturation adsorption capabilities of indium(III) and gallium(III) were evaluated as 47.2 and 31.0 mg/g or 0.41 and 0.44 mmol/g, respectively. The molar ratio of metal ion: P507 reagent on resin was about 1:3. Loaded resins can be regenerated, and the metals can be recovered selectively. Two fixed-bed columns arranged in-series were successfully used for the separation and recovery of these three metal ions from a multi-component solution. [Copyright &y& Elsevier]

Abstract: Assembly of InCl3 with 1,3,5-benzenetricarboxylic acid (H3btc) and pyridine or pyridine derivatives under hydrothermal conditions produces a series of isostructural coordination polymers with the interesting frameworks: {(HL)[In4(OH)4(btc)3]·L·3H2O} n , L=pyridine (1); L=2-picoline (2); L=4-picoline (3) and {(Hdpea)[In4(OH)4(btc)3]·3H2O} n (4) (dpea=1,2-di(4-pyridyl)ethane). In these four complexes, carboxyl and hydroxyl oxygen atoms bridge indium(III) centers to form octahedral chain-like sinusoidal curves, which are further interlinked by btc3− moieties to generate 3-D frameworks with 1-D channels. The protonated guests HL in 1–3 located at the channels can be fully exchanged by K+ ion or partially exchanged by Sr2+, and Ba2+ ions. [Copyright &y& Elsevier]

In an attempt to prepare pentacoordinate chlorobis( β-diketonato) gallium(III) and indium(III) complexes only the corresponding tris-products, Ga(PhCOCHCOPh)3 ( 1), Ga(tBuCOCHCOtBu)3 ( 1a), and In(PhCOCHCOPh)3 ( 2), could be isolated. The crystal and molecular structures of 1 and 2 were determined. Both the complexes were found to have triclinc crystal system, with P1 space group. Cell parameters: 1 – a = 9.913(3) Å, b = 10.534(6) Å, c = 18.05(2) Å, α = 93.86(5)°, β = 94.40(4)°, γ = 106.58(4)°, V = 1805(2) Å3, z = 2; 2 – a = 10.507(3) Å, b = 11.448(3) Å, c = 16.322(4) Å, α = 107.38(2)°, β = 97.38(2)°, γ = 102.23(2)°, V = 1792(1) Å3, z = 2. [ABSTRACT FROM AUTHOR]

Thallium(I) bis-oxalatodiaquaindate(III) monohydrate was obtained by precipitation of indium(III) withoxalic acid from slightly acidic solution in the presence of thallium(I). The complex was subjected to chemical analysis. The thermal decomposition behavior of the complex was studied using TG, DTA and DTG techniques. The solid complex salt and the intermediate product of its thermal decomposition were characterized using IR absorption and X-ray diffraction spectra. Based on data from these physicochemical investigations the structural formula of the complex was proposed as Tl[In (C2O4)2 (H2O)2]⋅H2O. [ABSTRACT FROM AUTHOR]

Disordered [InF 5 (H 2 O)]2– anion and (β- AlaH)+ cation in the structure of (β- AlaH) 2 [InF 5 (H 2 O)]·2H 2 O appear on the left. The dependences of the NMR spectra width ΔH½ for (β -AlaH)[InF 4 (H 2 O) 2 ]∙0.5H 2 O and (β- AlaH) 2 [InF 5 (H 2 O)]·2H 2 O compounds vs temperature are shown on the right. • Indium(III) fluoride complexes with β -alanine amino acid were synthesized for the first time. • The complexes were investigated by the methods of X-ray diffraction, 19F, 1H NMR spectroscopy, thermogravimetry, and DSC. • Disordered structures of β -alaninium cations with different carboxylic group structures were established. Indium(III) fluoride complexes with β -alanine amino acid (β- AlaH)[InF 4 (H 2 O) 2 ]·0.5H 2 O and (β- AlaH) 2 [InF 5 (H 2 O)]·2H 2 O have been synthesized for the first time and investigated by the methods of single crystal X-ray diffraction, 19F, 1H NMR spectroscopy, thermogravimetry (TG, DTG, DTA), and DSC. The crystal structure of (β- AlaH)[InF 4 (H 2 O) 2 ]·0.5H 2 O has been investigated at 296 K, whereas that of (β- AlaH) 2 [InF 5 (H 2 O)]·2H 2 O – at 173 K. The structure of (β- AlaH) 2 [InF 5 (H 2 O)]·2H 2 O was found to be disordered. Two disordered "resonance" structures of the β -alaninium cation with different arrangement of the proton in the carboxylic groups were obtained. The thermal behavior and character of ionic motions in the investigated compounds have been studied. [ABSTRACT FROM AUTHOR]

Indium(III) is extracted from HCl solutions (0.1–6 M HCl) by the ionic liquid (A324H+)(Cl−). The ionic liquid was generated in a previous reaction of the tertiary amine Hostarex A324 (triisooctyl amine) dissolved in Solvesso 100 with 1 M HCl solution. The metal extraction was investigated under various experimentalconditions: equilibration time, temperature, metal and HClconcentrations in the aqueous solution and ionic liquid concentration in the organic solution. Experimental results suggested that the indium extraction is due to an anionic exchange reaction between the chloride ion of the ionic liquid and the InCl 4 − of the aqueous solution. The performance of the system was compared against the extraction of other metals in binary solution (indium and accompanying metal) and against other ionic liquids. Indium(III) was stripped from metal-loaded organic solutions by the use of diluted hydrochloric acid solutions, and the precipitation of zero valent indium is possible by a further addition of sodium borohydride to the In-bearing strip solution. • The ionic liquid was generated by a simple acid-base chemical reaction. • Indium(III) extraction depended on the aqueous ionic strength. • The extraction of the metal corresponded to an anion exchange mechanism. • Indium(III) can be stripped from loaded organic phases by diluted HCl solutions. • Indium(III) is recovered as a mixture of the oxide and zero valent indium. [ABSTRACT FROM AUTHOR]

• A new type of indium(III) fluoride complex with In(III) atoms in the anion and cation was obtained. • The synthesized complex was studied by X-ray crystal diffraction and vibrational spectroscopy. • The first fluoride complex of indium(III) with an trivalent cation was obtained. A new type of fluoride complex of indium(III) [N(CH 3) 4 6 [In(H 2 O) 6 [InF 6 3 ·18H 2 O (1) containing In(III) atoms in the hexafluoride complex anion and the hexaaquacomplex cation has been synthesized and structurally studied. The structure of [N(CH 3) 4 6 [In(H 2 O) 6 [InF 6 3 ·18H 2 O is formed by isolated octahedral complex [In(1)F 6 3– and [In(2)F 6 3– anions, octahedral complex [In(3)(H 2 O) 6 3+ cations, [N(CH 3) 4 + cations, and crystallization H 2 O molecules. A formation in the structure of 1 of a rather strong O H···F hydrogen bond between the coordinated H 2 O molecules of the cation and F atoms of the complex anion with O···F distances of 2.472(1) Å has been established. The synthesized and structurally studied compound 1 is the obtained for the first time indium(III) fluoride complex containing a hexaaquacomplex [In(3)(H 2 O) 6 3+ cation having the configuration of a practically ideal octahedron. The vibrational spectra of the synthesized compound have been discussed with taking into account the results of crystal structure studies. [ABSTRACT FROM AUTHOR]