scholarly journals Revisiting the Assignment of Innocent and Non-Innocent Counter ions in Lanthanide(III) Solution Chemistry

2022 ◽  
Author(s):  
Nicolaj Kofod ◽  
Maria Storm Thomsen ◽  
Patrick Nawrocki ◽  
Thomas Just Sørensen
Keyword(s):  
Functional Materials ◽  
Outer Sphere ◽  
Solution Chemistry ◽  
Luminescence Spectra ◽  
Charge Balance ◽  
Solution Processes ◽  
Counter Ions ◽  
Display Technology ◽  
Lanthanides Complexes ◽  
Directional Bonding

Lanthanides are found in critical applications from display technology to renewable energy. Often these rare earth elements are used as alloys or functional materials, yet the access to them are trough solution processes. In aqueous solution the rare earths are found predominantly as trivalent ions and charge balance dictates that counter ions are present. The fast ligand exchange and lack of directional bonding in lanthanides complexes has led to questions regarding the speciation of Ln3+ solvates in the presence of various counter ions, and to the distinction between innocent = non-coordinating, and non-innocent = coordinating counter ions. There is limited agreement as to which counter ions that belong to each group, which lead to this report. By using Eu3+ luminescence, it was possible to clearly distinguish between coordinating and non-coordinating ions. To interpret the results it was required to bridge the descriptions of ion pairing and coordination. The da-ta—in form of Eu3+ luminescence spectra and luminescence lifetimes from solutions with varying concentrations of acetate, chloride, nitrate, fluoride, sulfate, perchlorate and triflate—were contrasted to those obtained with ethylenediaminetet-raaceticacid (EDTA), which allowed for the distinction between three Ln3+-anion interaction types. It was possible to con-clude which counter ions are truly innocent (e.g. ClO4- and OTf-), and which clearly coordinate (e.g. NO3- and AcO-). Finally, the considerate amount of data from systems studied under similar conditions allowed the minimum perturbation arising from inner sphere or outer sphere coordination in Eu3+ complexes to be identified.

Inorganic solution chemistry at elevated pressures

1995 ◽  
Vol 73 (5-6) ◽  
pp. 258-266 ◽  
Author(s):  
T. W. Swaddle
Keyword(s):  
Reduction Process ◽  
Outer Sphere ◽  
Solution Chemistry ◽  
Pressure Effects ◽  
Inorganic Systems ◽  
Oxidation Reduction ◽  
Adiabatic Electron Transfer ◽  
Pressure Independent ◽  
Experimental Values ◽  
Dissociative Processes

Recent interest in pressure effects on inorganic systems in solution has been centred upon the use of volumes of activation ΔV‡ as criteria of reaction mechanism. Work in our laboratory has sought to determine whether ΔV‡ is indeed a useful parameter in this respect, i.e., whether it is substantially independent of pressure and reaction conditions and whether it can be quantitatively predicted for suitably "simple" reactions. For solvent exchange on metal ions (the simplest conceivable substitution process), a semi-empirical model predicts ΔV‡ for limiting dissociative (bond breaking) and associative (bond making) mechanisms in water, but experimental values lie between these extremes, vindicating the Langford–Gray "interchange" model in which associative and dissociative processes are viewed as being concerted. For adiabatic electron transfer reactions of the outer-sphere type (the simplest conceivable oxidation–reduction process) in water, an adaptation of Marcus theory accounts for the essentially pressure-independent ΔV‡ satisfactorily, and failures of such predictions can be ascribed to complications such as nonadiabaticity or the incursion of inner-sphere (ligand-bridged) reaction pathways. The theory is less successful in nonaqueous solvents. Experimental methods used for these and related studies include high pressure adaptations of nuclear magnetic resonance, UV–visible spectrophotometry, stopped-flow techniques, cyclic voltammetry, and sampling under pressure.

scholarly journals Creation of POM complexes with multiple bonds between typical elements and transition metals and control of self-assembly

Impact ◽  
2020 ◽  
Vol 2020 (4) ◽  
pp. 33-35
Author(s):  
Koichi Nagata
Keyword(s):  
Self Assembly ◽  
Functional Materials ◽  
Molecular Ions ◽  
Solution Chemistry ◽  
Catalytic Reactions ◽  
Chemical Bonds ◽  
Multiple Bonds ◽  
Modern Life ◽  
Speed Up ◽  
And Control

The strongest materials on the planet, when viewed at a small of scale are all just molecules and atoms arranged in a particular order and held together by chemical bonds. Strength, flexibility and conductivity are all properties determined by the atomic structure of a given material. Chemists have long understood how different materials will interact to form new ones in reactions and this has advanced many discoveries and products in the industrial space. As an example, electronics, batteries and display screens all rely on materials that can take and receive electrons into their chemical bonds. This gives them the functionality to transmit and store electricity, and change colour and brightness at the push of a button. Other materials that support our modern life are magnetic, light absorbing or involve catalytic reactions, meaning they speed up the reaction of other materials, which greatly increases the yield and/or speed of the reaction. Catalysts are incredibly important for the manufacturing of many materials, and new elements that can perform these functions are highly sought after. Professor Koichi Nagata is based in the Department of Chemistry at Tohoku University, Japan, and is an expert in the field of solution chemistry, the aim of his research is to design and synthesise ubiquitous metal oxides that are abundant in the earth's crust as molecular ions to create crystalline solids by precisely arranging them to form hierarchical functional materials.

Sorption of Eu(III) at feldspar/water interface: effects of pH, organic matter, counter ions, and temperature

2017 ◽  
Vol 105 (12) ◽  
Author(s):  
Ping Li ◽  
Hanyu Wu ◽  
Jianjun Liang ◽  
Zhuoxin Yin ◽  
Duoqiang Pan ◽  
...  
Keyword(s):  
Organic Matter ◽  
Outer Sphere ◽  
Potassium Feldspar ◽  
Low Ph ◽  
High Ionic Strength ◽  
Counter Ions ◽  
Effects Of Ph ◽  
Alkaline Conditions ◽  
Ph Range ◽  
Interface Effects

AbstractThe sorption of Eu(III) on potassium feldspar (K-feldspar) was studied under various physicochemical conditions such as pH, temperature, counter ions and organic matter. The results showed that the sorption of Eu(III) on K-feldspar significantly increased with the increase of pH, and high Eu(III) concentration can inhibit such immobility to some extent. The presence of humic acid (HA) can increase the sorption of Eu(III) on K-feldspar in low pH range; while inhibit to a large extent under alkaline conditions. It is very interesting that at pH ~6.5, high ionic strength can promote the sorption of Eu(III) on K-feldspar in the presence of HA. In contrast, Eu(III) sorption was restricted obviously by NaCl in the absence of HA. The sorption procedure was involved with ion exchange and/or outer-sphere complexation as well as inner-sphere complexation. The presence of F

scholarly journals Crystal structure of poly[bis(ammonium) [bis(μ4-benzene-1,3,5-tricarboxylato)dizincate] 1-methylpyrrolidin-2-one disolvate]

2016 ◽  
Vol 72 (5) ◽  
pp. 764-767 ◽  
Author(s):  
Carlos Ordonez ◽  
Marina S. Fonari ◽  
Qiang Wei ◽  
Tatiana V. Timofeeva
Keyword(s):  
Metal Organic Framework ◽  
Solvent Molecule ◽  
Three Dimensional ◽  
Outer Sphere ◽  
Charge Balance ◽  
Coordination Environment ◽  
Secondary Building Units ◽  
Metal Organic ◽  
Solvent Molecules ◽  
Anionic Framework

The title three-dimensional metal–organic framework (MOF) compound, {(NH4)2[Zn2(C9H3O6)2]·2C5H9NO}n, features an anionic framework constructed from Zn2+cations and benzene-1,3,5-tricarboxylate (BTC) organic anions. Charge balance is achieved by outer sphere ammonium cations formed by degradation of di-n-butylamine in the solvothermal synthesis of the compound. Binuclear {Zn2(COO)2} entities act as the framework's secondary building units. Each ZnIIatom has a tetrahedral coordination environment with an O4set of donor atoms. The three-dimensional framework adopts a rutile-type topology and channels are filled in an alternating fashion with ordered and disordered 1-methylpyrrolidin-2-one solvent molecules and ammonium cations. The latter are held in the channelsviafour N—H...O hydrogen bonds, including three with the benzene-1,3,5-tricarboxylate ligands of the anionic framework and one with a 1-methylpyrrolidin-2-one solvent molecule.

scholarly journals Polysomatic apatites

2010 ◽  
Vol 66 (1) ◽  
pp. 1-16 ◽  
Author(s):  
Tom Baikie ◽  
Stevin S. Pramana ◽  
Cristiano Ferraris ◽  
Yizhong Huang ◽  
Emma Kendrick ◽  
...  
Keyword(s):  
State Of The Art ◽  
Functional Materials ◽  
Abundant Species ◽  
Complex Structures ◽  
Charge Balance ◽  
Principal Characteristics ◽  
X Ray ◽  
Structure Building ◽  
End Members ◽  
Stacking Disorder

Certain complex structures are logically regarded as intergrowths of chemically or topologically discrete modules. When the proportions of these components vary systematically a polysomatic series is created, whose construction provides a basis for understanding defects, symmetry alternation and trends in physical properties. Here, we describe the polysomatic family A 5N B 3N O9N + 6 X Nδ (2 ≤ N ≤ ∞) that is built by condensing N apatite modules (A 5 B 3O18 X δ) in configurations to create B n O3n + 1 (1 ≤ n ≤ ∞) tetrahedral chains. Hydroxyapatite [Ca10(PO4)6(OH)2] typifies a widely studied polysome where N = 2 and the tetrahedra are isolated in A 10(BO4)6 X 2 compounds, but N = 3 A 15(B 2O7)3(BO4)3 X 3 (ganomalite) and N = 4 A 20(B 2O7)6 X 4 (nasonite) are also known, with the X site untenanted or partially occupied as required for charge balance. The apatite modules, while topologically identical, are often compositionally or symmetrically distinct, and an infinite number of polysomes is feasible, generally with the restriction being that an A:B = 5:3 cation ratio be maintained. The end-members are the N = 2 polysome with all tetrahedra separated, and N = ∞, in which the hypothetical compound A 5 B 3O9 X contains infinite, corner-connected tetrahedral strings. The principal characteristics of a polysome are summarized using the nomenclature apatite-(A B X)-NS, where A/B/X are the most abundant species in these sites, N is the number of modules in the crystallographic repeat, and S is the symmetry symbol (usually H, T, M or A). This article examines the state-of-the-art in polysomatic apatite synthesis and crystallochemical design. It also presents X-ray and neutron powder diffraction investigations for several polysome chemical series and examines the prevalence of stacking disorder by electron microscopy. These insights into the structure-building principles of apatite polysomes will guide their development as functional materials.

Discerning the effects of phosphate status on the metabolism of hybrid poplar

2019 ◽  
Vol 40 (2) ◽  
pp. 158-169
Author(s):  
Letitia M Da Ros ◽  
Raju Y Soolanayakanahally ◽  
Shawn D Mansfield
Keyword(s):  
Organic Acid ◽  
Metabolic Response ◽  
Hybrid Poplar ◽  
Growth Strategies ◽  
Charge Balance ◽  
Trade Offs ◽  
Counter Ions ◽  
Bud Set ◽  
Low Phosphorus ◽  
Similar Growth

Abstract Accumulation of phosphate in leaves as external environmental phosphate concentrations increase has been observed across the plant kingdom. The excess storage of anions, such as phosphate, has various metabolic trade-offs, including a corresponding influx of counter-ions to maintain charge balance and/or the reduction in organic acid content to maintain internal pH. The leaves and roots of four hybrid poplar genotypes were tested for differences in metabolic response to increasing external phosphate and further effects on patterns of anion resorption among hybrid poplar and willow were explored. Organic acid concentrations increased or remained constant across treatments, suggesting that metabolic adjustments were made in response to greater influxes of inorganic cations rather than a response to increasing phosphate. During senescence, the hybrid poplar Tristis had higher sulfate and organic acid resorption, while hybrid willow, AAFC-5, had higher phosphate resorption proficiencies, suggesting differing anion remobilization mechanisms. Furthermore, phosphate accumulation was shown to continue well after bud-set in poplar hybrids, which may contribute to the low phosphorus resorption efficiency. This indicates that closely related species, with similar growth strategies, show preferential resorption toward different nutrients.

The effects of acidic deposition on cation leaching from three deciduous forest canopies

1985 ◽  
Vol 15 (6) ◽  
pp. 1055-1060 ◽  
Author(s):  
Gary M. Lovett ◽  
Steven E. Lindberg ◽  
Daniel D. Richter ◽  
Dale W. Johnson
Keyword(s):  
Acidic Deposition ◽  
Deciduous Forest ◽  
Major Ions ◽  
Exchange Process ◽  
Charge Balance ◽  
Exchange Reactions ◽  
Cation Leaching ◽  
Counter Ions ◽  
Deposition Effect ◽  
A Charge

Canopy leaching or retention of all major ions was determined for three deciduous forests in eastern Tennessee that are currently receiving wet and dry acidic deposition. For all three canopies, the retention of atmospherically deposited cations (H+ and [Formula: see text]) exceeded retention of deposited anions [Formula: see text] on a charge-equivalent basis. Charge balance was maintained by ion exchange between the deposited cations and K+, Ca2+, and Mg2+ on the canopy surfaces. It was found that 40–60% of the leaching of K+, Ca2+, and Mg2+ from these canopies results from this exchange process, with the remainder attributable to coleaching with plant-derived anions. Because the cation exchange can be largely attributed to retention of deposited H+, we interpret it as a measure of the acidic deposition effect on foliar cation leaching. Dry deposition was found to be an important input for most of the major cations and anions. The data indicate that organic anions may be important counter ions to cation leaching, especially in the absence of acidic deposition, and that acid–base reactions in the canopy can obscure the true H+-exchange reactions between the deposition and the canopy.

scholarly journals Crystal structure of tris(trans-1,2-diaminocyclohexane-κ2N,N′)cobalt(III) trichloride monohydrate

2016 ◽  
Vol 72 (1) ◽  
pp. 49-52
Author(s):  
Megan K. Gallagher ◽  
Allen G. Oliver ◽  
A. Graham Lappin
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Outer Sphere ◽  
Complex Salt ◽  
Coordination Complexes ◽  
Water Molecules ◽  
Rotation Symmetry ◽  
Space Group ◽  
Solvent Water ◽  
Counter Ions

The synthesis of the title hydrated complex salt, [Co(C6H14N2)3]Cl3·H2O, from racemictrans-1,2-diaminocyclohexane and [CoCl(NH3)5]Cl2and its structural characterization are presented in this paper. The product was synthesized in the interest of understanding the hydrogen-bonding patterns of coordination complexes. Previous characterizations of the product in theI-42dspace group have not yielded coordinates; thus, this paper provides the first coordinates for this complex in this space group. The octahedrally coordinated cation adopts twofold rotation symmetry, with outer-sphere chloride counter-ions and solvent water molecules forming a hydrogen-bonded network with amine H atoms.

High Resolution Electron Microscopy of internal interfaces in layered materials

1990 ◽  
Vol 48 (4) ◽  
pp. 320-321
Author(s):  
Yoichi Ishida ◽  
Hideki Ichinose ◽  
Yutaka Takahashi ◽  
Jin-yeh Wang
Keyword(s):  
Grain Boundaries ◽  
Mirror Symmetry ◽  
Functional Materials ◽  
High Resolution Electron Microscopy ◽  
Layered Materials ◽  
Plane Boundary ◽  
Chemical Information ◽  
Layer Plane ◽  
High Tc ◽  
Cubic Metals

Layered materials draw attention in recent years in response to the world-wide drive to discover new functional materials. High-Tc superconducting oxide is one example. Internal interfaces in such layered materials differ significantly from those of cubic metals. They are often parallel to the layer of the neighboring crystals in sintered samples(layer plane boundary), while periodically ordered interfaces with the two neighboring crystals in mirror symmetry to each other are relatively rare. Consequently, the atomistic features of the interface differ significantly from those of cubic metals. In this paper grain boundaries in sintered high-Tc superconducting oxides, joined interfaces between engineering ceramics with metals, and polytype interfaces in vapor-deposited bicrystal are examined to collect atomic information of the interfaces in layered materials. The analysis proved that they are not neccessarily more complicated than that of simple grain boundaries in cubic metals. The interfaces are majorly layer plane type which is parallel to the compound layer. Secondly, chemical information is often available, which helps the interpretation of the interface atomic structure.

Sign in / Sign up

Export Citation Format

Share Document