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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,495 records · Page 83
All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

High-Performing, Low-Temperature-Operating, Long-Lifetime Aerospace Lubricants

Long-duration space exploration will require spacecraft systems that can operate effectively over several years with minimal or no maintenance. Aerospace lubricants are key components of spacecraft systems. Physical Sciences Inc., has synthesized and characterized novel ionic liquids for use in aerospace lubricants that contribute to decreased viscosity, friction, and wear in aerospace systems. The resulting formulations offer low vapor pressure and outgassing properties and thermal stability up to 250 C. They are effective for use at temperatures as low as -70 C and provide long-term operational stability in aerospace systems. In Phase II, the company scaled several new ionic liquids and evaluated a novel formulation in a NASA testbed. The resulting lubricant compounds will offer lower volatility, decreased corrosion, and better tribological characteristics than standard liquid lubricants, particularly at lower temperatures.

Joshi, Prakash↗
DOE OSTI2021

Polymers in molten inorganic salt hydrate phase change materials: solubility and gelation

Inorganic salt hydrates are of interest as phase change materials (PCMs) for thermal energy storage because of their unique properties, such as high latent heats of fusion, moderate melting temperatures, high volumetric energy storage densities, and enhanced thermal conductivities compared to their organic counterparts. Because of the low viscosities of molten salt hydrates, the leakage and settling of solids can easily occur during their application. Polymers are promising candidates for preventing these issues. In addition, the non-flammability, non-volatility, and nontoxicity of many molten salt hydrates make them attractive options as “green” solvents for polymers. However, solutions of polymers in molten salt hydrates have rarely been studied and are poorly understood. The highly ionic environments in these materials created due to a scarcity of hydration water for ions leads to strong ionic interactions, with ramifications for polymer solubility and chain expansion. This Perspective article aims to focus on polymer solutions and gels in inorganic salt hydrates by comparing these systems with existing knowledge of polymers in traditional ionic liquids and aqueous salt solutions. To provide insight into the states of ions and water in molten salt hydrates and the degree of hydration of polymers in these solvents, infrared spectroscopy experiments have been performed, and the data are correlated with the temperature-responsive gelation of poly(vinyl alcohol), one candidate material currently used for the shape stabilization of inorganic PCMs. Finally, the thermal properties of inorganic salt hydrates and ionic liquids are compared and strategies for the shape stabilization of inorganic salt hydrates using polymers, through the formation of physical gels, are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Super p-sulfur cathodes for quasi-solid-state lithium-sulfur-batteries

Lithium-Sulfur (Li-S) batteries have become a promising candidate to meet the current energy storage demand, with its natural abundance of materials, high theoretical capacity of 1672 mAhg-1, high energy density of 2600 Whkg-1, low cost and lower environmental impact. Sulfide based solid state electrolytes (SSEs) have received greater attention due to their higher ionic conductivity, compatible interface with sulfur-based cathodes, and lower grain boundary resistance. However, the interface between SSEs and cathodes has become a challenge in all solid-state Li-S batteries due to the rigidity of the participating surfaces. A hybrid electrolyte containing SSE coupled with a small amount of ionic liquid, was essential to improve the interface contact of the SSE with the electrodes. Coating-based cathodes were successfully fabricated using water-based carboxymethyl cellulose (CMC) solution and Styrene butadiene rubber (SBR) as the binder with low sulfur loading (0.70 mgcm-2) as well as high sulfur loading (4.0 mgcm-2). Solid-state composite powder-based cathodes pressed onto SSE (loading 4.0 mgcm-2) with enhanced electronic and ionic conductivity were fabricated with Super P: Sulfur (SP:S) and SSE. Ionic Liquids (IL) prepared using Lithium bis(trifluoromethyl sulfonyl)imide (LiTFSI) as salt, with premixed pyrrolidinium bis(trifluoromethyl sulfonyl)imide (PYR) as solvent and 1,3-dioxolane (DOL) as diluent were used to wet both SSE-electrode interfaces. The effect of IL dilution, co-solvent amount, LiTFSI concentration, C rate at which the batteries are tested and the effect of SSE inside the cathode, were systematically studied and optimized to develop a quasi-solid-state electrolyte Li-S battery (QSSLSB) with higher capacity retention and cyclability. LiTFSI (2M) dissolved in PYR:DOL(1:1) found to be optimum IL combination for low sulfur loading QSSLSBs reaching 500 mAh/g after 100 cycles while LiTFSI (3M) in PYR:DOL(1:3) was the optimum IL concentration for higher loading QSSLSBs reaching 400 mAh/g after 100 cycles. This work reports promising results of QSSLSB based on novel Li6PS5F0.5Cl0.5 Li-argyrodite solid-state electrolyte (SSE) with minute amount of IL, Super P-Sulfur (SP:S) cathode, and Li-anode. It also offers a new insight into the intimate interfacial contacts between the SSE and carbon-sulfur cathodes, which will be critical for improved electrochemical performance of quasi-solid-state lithium-sulfur batteries with high sulfur loading in the future.

25 ENERGY STORAGE↗
DOE OSTI2015

Refining the phylum Chlorobi by resolving the phylogeny and metabolic potential of the representative of a deeply branching, uncultivated lineage

Recent studies have expanded the phylum Chlorobi, demonstrating that the green sulfur bacteria (GSB), the original cultured representatives of the phylum, are a part of a larger lineage whose members have more diverse metabolic capabilities that overlap with members of the phylum Bacteroidetes. The 16S rRNA gene of an uncultivated clone, OPB56, distantly related to the phyla Chlorobi and Bacteroidetes, was recovered from Obsidian Pool in Yellowstone National Park; however, the detailed phylogeny and function of OPB56 and related clones have remained unknown. Culturing of thermophilic bacterial consortia from compost by adaptation to grow on ionic-liquid pretreated switchgrass provided a consortium in which one of the most abundant members, NICIL-2, clustered with OPB56-related clones. Phylogenetic analysis using the full-length 16S rRNA gene from NICIL-2 demonstrated that it was part of a monophyletic clade, referred to as OPB56, distinct from the Bacteroidetes and Chlorobi. A near complete draft genome ( > 95% complete) was recovered from metagenomic data from the culture adapted to grow on ionic-liquid pretreated switchgrass using an automated binning algorithm, and this genome was used for marker gene-based phylogenetic analysis and metabolic reconstruction. Six additional genomes related to NICIL-2 were reconstructed from metagenomic data sets obtained from thermal springs at Yellowstone National Park and Nevada Great Boiling Spring. In contrast to the 16S rRNA gene phylogenetic analysis, protein phylogenetic analysis was most consistent with the clustering of the Chlorobea, Ignavibacteria and OPB56 into a single phylum level clade. Metabolic reconstruction of NICIL-2 demonstrated a close linkage with the class Ignavibacteria and the family Rhodothermaceae, a deeply branching Bacteroidetes lineage. The combined phylogenetic and functional analysis of the NICIL-2 genome has refined the membership in the phylum Chlorobi and emphasized the close evolutionary and metabolic relationship between the phyla Chlorobi and the Bacteroidetes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Exchange Kinetics for a Single Block Copolymer in Micelles of Two Different Sizes

The effect of micellar size on the chain exchange kinetics in spherical micelles consisting of poly(methyl methacrylate)-block-poly(n-butyl methacrylate) (PMMA-b- PnBMA) in a mixture of ionic liquids (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIM][TFSI], and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)- imide, [BMIM][TFSI]) was investigated using time-resolved small-angle neutron scattering (TR-SANS). Two spherical micelles with different core sizes were prepared from a single block copolymer by using different protocols. In one case the micelles were formed in the presence of a cosolvent, while in the other a polymer thin film was directly dissolved in the ionic liquid. Interestingly, the micelle core size prepared from the latter method is ~30% larger than that obtained in the former case. TR-SANS experiments reveal that the rate of single chain exchange in the micelles with a larger core size is slowed down by ~3 times compared to the smaller core radius. We surmise this can be possibly attributed to the smaller interfacial area per chain, and larger corona density, for micelles with a larger core dimension. These geometrical factors can potentially lead to changes in both the attempt time and activation barrier for chain expulsion during the unimer exchange process. Our results clearly suggest that, in addition to the molecular characteristics of the block copolymer and solvent, the geometrical structure of the micelle plays an important role in the unimer dynamic exchange processes in block copolymer micelles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Relationship between sugarcane culm and leaf biomass composition and saccharification efficiency

Background: Lignocellulosic biomass is recognized as a promising renewable feedstock for the production of biofuels. However, current methods for converting biomass into fermentable sugars are considered too expensive and inefficient due to the recalcitrance of the secondary cell wall. Biomass composition can be modified to create varieties that are efficiently broken down to release cell wall sugars. This study focused on identifying the key biomass components influencing plant cell wall recalcitrance that can be targeted for selection in sugarcane, an important and abundant source of biomass. Results: Biomass composition and the amount of glucan converted into glucose after saccharification were measured in leaf and culm tissues from seven sugarcane genotypes varying in fiber composition after no pretreatment and dilute acid, hydrothermal and ionic liquid pretreatments. In extractives-free sugarcane leaf and culm tissue, glucan, xylan, acid-insoluble lignin (AIL) and acid-soluble lignin (ASL) ranged from 20 to 32%, 15% to 21%, 14% to 20% and 2% to 4%, respectively. The ratio of syringyl (S) to guaiacyl (G) content in the lignin ranged from 1.5 to 2.2 in the culm and from 0.65 to 1.1 in the leaf. Hydrothermal and dilute acid pretreatments predominantly reduced xylan content, while the ionic liquid (IL) pretreatment targeted AIL reduction. The amount of glucan converted into glucose after 26 h of pre-saccharification was highest after IL pretreatment (42% in culm and 63.5% in leaf) compared to the other pretreatments. Additionally, glucan conversion in leaf tissues was approximately 1.5-fold of that in culm tissues. Percent glucan conversion varied between genotypes but there was no genotype that was superior to all others across the pretreatment groups. Path analysis revealed that S/G ratio, AIL and xylan had the strongest negative associations with percent glucan conversion, while ASL and glucan content had strong positive influences. Conclusion: To improve saccharification efficiency of lignocellulosic biomass, breeders should focus on reducing S/G ratio, xylan and AIL content and increasing ASL and glucan content. This will be key for the development of sugarcane varieties for bioenergy uses.

09 BIOMASS FUELS↗
DOE OSTI2025

Alkali Cation Inhibition of Imidazolium-Mediated Electrochemical CO 2 Reduction on Silver

Imidazolium-based ionic liquids have led to enhanced CO 2 electroreduction activity due to cation effects at the cathode surface, stabilizing the reaction intermediates and decreasing the activation energy. In aqueous media, alkali cations are also known to improve CO 2 reduction activity on metals such as Ag, with the enhancement attributed to electrical double layer effects and trending with the size of the alkali cation. However, the effect of a mixed catholyte solution of alkali cations in the presence of an imidazolium-based ionic liquid has not been well-explored. Herein, 1-ethyl-3-methylimidazolium tetrafluoroborate, [EMIM][BF 4 ], in water was investigated with alkali salts to unravel the interaction effects for CO 2 electroreduction on Ag. Although both [EMIM] + and alkali cations have individually improved CO 2 to CO conversion on Ag in water, electrochemical results showed that alkali cations hindered imidazolium-mediated CO 2 electroreduction in most conditions. Li + , in particular, was sharply inhibitory compared to other alkali cations and strongly redirected the selectivity to hydrogen evolution. The nature of the alkali cation inhibition was investigated with spectroscopic techniques, including in situ surface-enhanced Raman spectroscopy (SERS) and dynamic electrochemical impedance spectroscopy (DEIS). Along with computational insights from density functional theory (DFT), the electrochemical and spectroscopic data suggest that alkali cations inhibit [EMIM]-mediated CO 2 reduction by competing for surface adsorption sites, preventing the potential-dependent structural reorientation of imidazolium, and promoting hydrogen evolution by bringing solvated water to the cathode surface.

cations↗
DOE OSTI2022

Correlation between Redox Potential and Solvation Structure in Biphasic Electrolytes for Li Metal Batteries

The activity of lithium ions in electrolytes depends on their solvation structures. However, the understanding of changes in Li + activity is still elusive in terms of interactions between lithium ions and solvent molecules. Herein, the chelating effect of lithium ion by forming [Li(15C5)] + gives rise to a decrease in Li + activity, leading to the negative potential shift of Li metal anode. Moreover, weakly solvating lithium ions in ionic liquids, such as [Li(TFSI) 2 ] - (TFSI = bis(trifluoromethanesulfonyl)imide), increase in Li + activity, resulting in the positive potential shift of LiFePO 4 cathode. This allows the development of innovative high energy density Li metal batteries, such as 3.8 V class Li | LiFePO 4 cells, along with introducing stable biphasic electrolytes. In addition, correlation between Li + activity, cell potential shift, and Li + solvation structure is investigated by comparing solvated Li + ions with carbonate solvents, chelated Li + ions with cyclic and linear ethers, and weakly solvating Li + ions in ionic liquids. These findings elucidate a broader understanding of the complex origin of Li + activity and provide an opportunity to achieve high energy density lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Reversible Electron-Beam Patterning of Colloidal Nanoparticles at Fluid Interfaces

The directed self-assembly of colloidal nanoparticles (NPs) using external fields guides the formation of sophisticated hierarchical materials but becomes less effective with decreasing particle size. As an alternative, electron-beam-driven assembly offers a potential avenue for targeted nanoscale manipulation, yet remains poorly controlled due to the variety and complexity of beam interaction mechanisms. Here, we investigate the beam–particle interaction of silica NPs pinned to the fluid–vacuum interface of ionic liquid droplets. In these experiments, scanning electron microscopy of the droplet surface resolves NP trajectories over space and time while simultaneously driving their reorganization. With this platform, we demonstrate the ability to direct particle transport and create transient, reversible colloidal patterns on the droplet surface. By tuning the beam voltage, we achieve precise control over both the strength and sign of the beam–particle interaction, with low voltages repelling particles and high voltages attracting them. This response stems from the formation of well-defined solvent flow fields generated from trace radiolysis of the ionic liquid, as determined through statistical analysis of single-particle trajectories under varying solvent composition. Altogether, electron-beam-guided assembly introduces a versatile strategy for nanoscale colloidal manipulation, offering new possibilities for the design of dynamic, reconfigurable systems with applications in adaptive photonics and catalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Cathode based on molybdenum disulfide nanoflakes for lithium-oxygen batteries.

Lithium-oxygen (Li-O-2) batteries have been recognized as an emerging technology for energy storage systems owing to their high theoretical specific energy. One challenge is to find an electrolyte/cathode system that is efficient, stable, and cost-effective. We present such a system based on molybdenum disulfide (MoS2) nanoflakes combined with an ionic liquid (IL) that work together as an effective cocatalyst for discharge and charge in a Li-O-2 battery. Cyclic voltammetry results show superior catalytic performance for this cocatalyst for both oxygen reduction and evolution reactions compared to Au and Pt catalysts. It also performs remarkably well in the Li-O-2 battery system with 85% round-trip efficiency and reversibility up to 50 cycles. Density functional calculations provide a mechanistic understanding of the MoS2 nanoflakes/IL system. cocatalyst reported in this work could open the way for exploiting the unique properties of ionic liquids in Li-air batteries in combination with nanostructured MoS2 as a cathode material.

Asadi, Mohammad↗
DOE OSTI2016

What can molecular simulation do for global warming?

Carbon capture is necessary to reduce CO 2 emissions from burning fossil fuels, which has led to global warming. Molecular simulations offer chemical insights and design principles for new separation media and for understanding the separation process. In this review, we summarize recent applications of simulation methods from ab initio and density functional theory to classical molecular dynamics and Grand canonical Monte Carlo in understanding ionic liquids and porous carbonaceous materials for CO 2 separation, especially the postcombustion CO 2 / N 2 separation. We highlight design and simulation of the porous two‐dimensional ( 2D ) materials as the highly selective membranes for CO 2 separation. Simulated structure–property relationships for the materials are discussed in connection to the corresponding chemisorption, physisorption, or membrane process. In chemisorption, the focus is on reducing the heat of reaction with CO 2 ; in physisorption, the key is to increase the binding strength via CO 2 ‐philic groups; in membrane process, the key is to increase solubility for ionic‐liquid membranes and to control pore size for 2D materials. Challenges and opportunities for simulating emerging materials are also discussed. WIREs Comput Mol Sci 2016, 6:173–197. doi: 10.1002/wcms.1241 This article is categorized under: Structure and Mechanism > Computational Materials Science Electronic Structure Theory > Density Functional Theory Molecular and Statistical Mechanics > Molecular Interactions

Tian, Ziqi↗
DOE OSTI2014

Electrolyte materials - Issues and challenges

Electrolytes are vital components of an electrochemical energy storage device. They are usually composed of a solvent or mixture of solvents and a salt or a mixture of salts which provide the appropriate environment for ionic conduction. One of the main issues associated with the selection of a proper electrolyte is that its electronic properties have to be such that allow a wide electrochemical window - defined as the voltage range in which the electrolyte is not oxidized or reduced - suitable to the battery operating voltage. In addition, electrolytes must have high ionic conductivity and negligible electronic conductivity, be chemically stable with respect to the other battery components, have low flammability, and low cost. Weak stability of the electrolyte against oxidation or reduction leads to the formation of a solid-electrolyte interphase (SEI) layer at the surface of the cathode and anode respectively. Depending on the materials of the electrolyte and those of the electrode, the SEI layer may be composed by combinations of organic and inorganic species, and it may exert a passivating role. In this paper we discuss the current status of knowledge about electrolyte materials, including non-aqueous liquids, ionic liquids, solid ceramic and polymer electrolytes. We also review the basic knowledge about the SEI layer formation, and challenges for a rational design of stable electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2017

Dealloying, Microstructure and the Corrosion/Protection of Cast Magnesium Alloys

The purpose of this project was to develop a greater understanding of micro-galvanic corrosion effects in cast magnesium alloys using both experimental and computational methods. Experimental accomplishments have been made in the following areas of interest: characterization, aqueous free-corrosion, atmospheric corrosion, ionic liquid dissolution, rate kinetics of oxide dissolution, and coating investigation. Commercial alloys (AZ91D, AM60, and AZ31B), binary-phase alloys (αMg-2at.%Al, αMg-5at.%Al, and Mg-8at.%Al), and component phases (Mg, Al, β-Mg, β-1%Zn, MnAl3) were obtained and characterized using energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Full immersion in aqueous chloride was used to characterize the corrosion behavior of alloys. Rotating disc electrodes (RDEs) were used to observe accelerated long-term corrosion behavior. Al surface redistribution for freely corroded samples was analyzed using SEM, EDS, and lithium underpotential deposition (Li UPD). Atmospheric corrosion was observed using contact angle evolution, overnight pH monitoring, and surface pH evolution studies. Ionic liquid corrosion characterization was performed using linear sweep voltammetry and potentiostatic dissolution in 150° choline chloride-urea (cc-urea). Two surface coatings were investigated: (1) Li-carbonate and (2) cc-urea. Li-carbonate coatings were characterized using X-ray photoelectron spectroscopy (XPS), SEM, and aqueous free corrosion potential monitoring. Hydrophobic cc-urea coatings were characterized using contact angle measurements and electrochemical impedance spectroscopy. Oxide dissolution rate kinetics were studied using inductively coupled plasma mass spectroscopy (ICP-MS). Computational accomplishments have been made through the development of Kinetic Monte Carlo (KMC) simulations which model time- and composition-dependent effects on the microstructure due to spatial redistribution of alloying elements during corrosion.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Corrosion of Commercial Mg–Al Alloys: AZ31B, AM60, and AZ91D

Aqueous corrosion, atmospheric corrosion, and ionic liquid dissolution studies were performed on commercial alloys AZ31B, AM60, and AZ91D and compared with previously reported results for single-phase binary Mg–Al alloys containing similar Al concentrations (αMg-2 at% Al, αMg-5 at% Al, and Mg-8 at% Al). Polarization studies in 0.6 M NaCl were used to characterize the aqueous free corrosion behavior during 20-h free immersion. Accelerated corrosion testing was performed using a rotating-disk electrode which revealed the evolution of an Al-rich mud-cracking and platelet morphology. Atmospheric droplet testing showed rapid pH increases that depended on the Al concentration in the alloy. Time-dependent contact angle measurements showed that the degree of droplet wetting increased during free corrosion by ~50° over 20 h in 0.6 M NaCl. Ionic liquid dissolution studies in 1:2 M choline chloride:urea deep eutectic solvent were performed in order to examine the current-voltage behavior of these alloys in the absence of water and hydrogen reduction. The results of these studies revealed the formation of nanowire corrosion morphologies within a honeycomb lattice structure which we attribute to selective dissolution of Mg via a two-dimensional stepflow process

25 ENERGY STORAGE↗
DOE OSTI2016

Influence of Surface Oxidation on Ion Dynamics and Capacitance in Porous and Nonporous Carbon Electrodes

We investigate the influence of surface chemistry and ion confinement on capacitance and electrosorption dynamics of room-temperature ionic liquids (RTILs) in supercapacitors. Using air oxidation and vacuum annealing, we produced defunctionalized and oxygen-rich surfaces of carbide-derived carbons (CDCs) and graphene nanoplatelets (GNPs). While oxidized surfaces of porous CDCs improve capacitance and rate handling abilities of ions, defunctionalized nonporous GNPs improve charge storage densities on planar electrodes. Quasi-elastic neutron scattering (QENS) and inelastic neutron scattering (INS) probed the structure, dynamics, and orientation of RTIL ions confined in divergently functionalized pores. Oxidized, ionophilic surfaces draw ions closer to pore surfaces and enhance potential-driven ion transport during electrosorption. Molecular dynamics (MD) simulations corroborated experimental data and demonstrated the significance of surface functional groups on ion orientations, accumulation densities, and capacitance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Conversion of depolymerized sugars and aromatics from engineered feedstocks by two oleaginous red yeasts

One of the requirements for efficient biological conversion of lignocellulose to bioproducts is the compatibility of biological catalysts with the processes employed to solubilize and depolymerize the lignocellulosic components. The red yeasts Rhodosporidium toruloides and Rhodotorula mucilaginosa were evaluated for their ability to assimilate sugars and aromatic compounds extracted from two engineered lines of Arabidopsis thaliana with modified lignin or the wild-type using ionic liquid, acid or alkaline pretreatments. Differential amounts of monomeric sugars, organic acids and, in the case of the engineered lines, either 4-hydroxybenzoic or protocatechuic acid were additionally released from the biomass and found to be tolerated and consumed by both microorganisms. Genetically-engineered strains of the two red yeasts successfully converted the depolymerized products into the biofuel precursor bisabolene when cultivated on hydrolysates or synthetic media containing specific sugars, acids and aromatics found in the hydrolysates.

Rodriguez, Alberto↗
DOE OSTI2021

Anhydrous vs Hydrated f-Element Acetate Polymers Dictated by the Stoichiometry of Protic Acidic/Basic Azole Mixtures

Continuing our investigations of ionic liquid (IL) based routes to a library of f-element/soft donor complexes which could be studied crystallographically, we have explored the dissolution of f-element salts in protic imidazole-based ILs containing only soft donors at high temperatures to drive off volatiles, including water and carboxylic or mineral acids. Here we present our results, reacting acidic and basic azoles in 1:3 or 1:1 stoichiometric compositions at elevated temperature, followed by saturation with Nd(OAc) 3 ·xH 2 O or Ce(OAc) 3 ·xH 2 O, which led to 13 new metal–acetate polymeric complexes identified by single-crystal X-ray diffraction. We found that the diversity in coordination modes of the simple acetate ligand that interfere with substitution of the softer N donors led to several readily crystallizable complexes forming two distinct groups with respect to f-element interaction with the ionic liquid precursors. When the acidic/basic azole ratio was 1:3, acetate and a neutral basic azole were found to be coordinated to the metal centers but no water, although in one case (2) water was observed in the secondary coordination sphere: [Ce(μ 2 -OAc) 3 (C 1 im)] n (1, C 1 im = 1-methylimidazole), [Nd(μ 2 -(OAc) 3 (C 1 im)] n ·nH 2 O (2), [Ce(μ 2 -OAc) 3 (C 2 im)] n (3, C 2 im = 1-ethylimidazole), [Ln(μ 2 -OAc) 3 DMF] n (Ln = Nd (4), Ce (5); dimethylformamide (DMF) was substituted for the azole mixture), and [Nd(μ 2 -OAc) 3 (C 4 im)] n (6, C 4 im = 1-butylimidazole). However, when the stoichiometric ratio was 1:1, water was always observed coordinated to the metal ions with the acidic azole included in the structure as a solvate or cocrystal, despite a higher reaction temperature: [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(1,2,3-Taz) (7, 1,2,3-Taz = 1,2,3-triazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(4,5-DCim) (Ln = Nd (8), Ce (9), 4,5-DCim = 4,5-dicyanoimidazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(3,5-diNH 2 -1,2,4-Taz) (Ln = Nd (10), Ce (11), 3,5-diNH 2 -1,2,4-Taz = 3,5-diamino-1,2,4-triazole), [Ce(μ 2 -OAc) 3 (OH 2 )] n ·n(3-NH 2 -1,2,4-Taz) (12, 3-NH 2 -1,2,4-Taz = 3-amino-1,2,4-triazole), and [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(5-NH 2 -Tz) (13, 5-NH2-Tz = 5-aminotetrazole). All of the compounds retain the Ln:OAc– ratio of 1:3 and form 1D polymeric chains; however, they exhibit a variety of coordination modes affecting the degree of chain condensation. The isolation of both hydrated and anhydrous products revealed different abilities of the investigated soft N-donors to compete with O-donors finding their place in the coordination sphere of the lanthanide or in the crystal lattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗