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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Synthesis of novel symmetrical macrocycle via oxidative homocoupling of bisalkyne

A novel symmetrical macrocycle has been synthesised via oxidative homocoupling of bisalkyne, diprop-2-ynyl pyridine-2,6-dicarboxylate mediated by copper (I) iodide (CuI) and 4-dimethylaminopyridine (DMAP). The precursor compound was synthesised from 2,6-pyridine dicarbonyl dichloride and propargyl alcohol in the presence of triethylamine. The reaction mixture was stirred overnight and further purified via column chromatograpy with 76% yield. Single crystal for X-ray study was obtained by recrystallization from acetone. Subsequently, a symmetrical macrocycle was synthesised from oxidative homocoupling of precursor compound in open atmosphere. The crude product was purified by column chromatography to furnish macrocycle compound with 5% yield. Both compounds were characterised by IR, {sup 1}H and {sup 13}C NMR and mass spectral techniques. The unusual conformation of the bisalkyne and twisted conformation of designed macrocycle has influence the percentage yield. This has been studied thoroughly by X-ray crystallography and electronic structure calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Water network-mediated, electron-induced proton transfer in [C{sub 5}H{sub 5}N ⋅ (H{sub 2}O){sub n}]{sup −} clusters

The role of proton-assisted charge accommodation in electron capture by a heterocyclic electron scavenger is investigated through theoretical analysis of the vibrational spectra of cold, gas phase [Py ⋅ (H{sub 2}O){sub n=3−5}]{sup −} clusters. These radical anions are formed when an excess electron is attached to water clusters containing a single pyridine (Py) molecule in a supersonic jet ion source. Under these conditions, the cluster ion distribution starts promptly at n = 3, and the photoelectron spectra, combined with vibrational predissociation spectra of the Ar-tagged anions, establish that for n > 3, these species are best described as hydrated hydroxide ions with the neutral pyridinium radical, PyH{sup (0)}, occupying one of the primary solvation sites of the OH{sup −}. The n = 3 cluster appears to be a special case where charge localization on Py and hydroxide is nearly isoenergetic, and the nature of this species is explored with ab initio molecular dynamics calculations of the trajectories that start from metastable arrangements of the anion based on a diffuse, essentially dipole-bound electron. These calculations indicate that the reaction proceeds via a relatively slow rearrangement of the water network to create a favorable hydration configuration around the water molecule that eventually donates a proton to the Py nitrogen atom to yield the product hydroxide ion. The correlation between the degree of excess charge localization and the evolving shape of the water network revealed by this approach thus provides a microscopic picture of the “solvent coordinate” at the heart of a prototypical proton-coupled electron transfer reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Effect of transition metal salts on the initiated chemical vapor deposition of polymer thin films

In this work, the effect of transition metal salts on the initiated chemical vapor deposition of polymer thin films was studied using x-ray photoelectron spectroscopy. The polymerizations of 4-vinyl pyridine and 1H,1H,2H,2H-perfluorodecyl acrylate were studied using copper(II) chloride (CuCl{sub 2}) and iron(III) chloride (FeCl{sub 3}) as the transition metal salts. It was found that the surface coverages of both poly(4-vinyl pyridine) (P4VP) and poly(1H,1H,2H,2H-perfluorodecyl acrylate) were decreased on CuCl{sub 2}, while the surface coverage of only P4VP was decreased on FeCl{sub 3}. The decreased polymer surface coverage was found to be due to quenching of the propagating radicals by the salt, which led to a reduction of the oxidation state of the metal. The identification of this reaction mechanism allowed for tuning of the effectiveness of the salts to decrease the polymer surface coverage through the adjustment of processing parameters such as the filament temperature. Additionally, it was demonstrated that the ability of transition metal salts to decrease the polymer surface coverage could be extended to the fabrication of patterned cross-linked coatings, which is important for many practical applications such as sensors and microelectronics.

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

Efficient Blue Phosphorescent OLEDs with Improved Stability and Color Purity through Judicious Triplet Exciton Management

Abstract Highly efficient and stable blue phosphorescent organic light‐emitting diodes are achieved by employing a step‐wise graded doping of platinum(II) 9‐(pyridin‐2‐yl)‐2‐(9‐(pyridin‐2‐yl)‐9 H ‐carbazol‐2‐yloxy)‐9 H ‐carbazole (PtNON) in a device setting. A device employing PtNON demonstrates a high peak external quantum efficiency (EQE) of 17.4% with an estimated LT 70 lifetime of over 1330 h at a brightness of 1000 cd m −2 . PtNON is then investigated as a “triplet sensitizer” in an alternating donor–acceptor doped emissive layer to further improve the device emission color purity by carefully managing an efficient Förster resonant energy transfer from PtNON to 2,5,8,11‐tetra‐ tert ‐butylperylene as a selected acceptor material. Thus, such OLED devices demonstrate an EQE of 16.9% with color coordinates of (0.16, 0.25) and an estimated luminance (LT 70 ) lifetime of 628 h at a high brightness of 1000 cd m −2 .

Klimes, Kody↗
DOE OSTI2024

Design Principles of Diketopyrrolopyrrole‐Thienopyrrolodione Acceptor 1 –Acceptor 2 Copolymers

Abstract The design principles of acceptor 1 –acceptor 2 copolymers featuring alternating diketopyrrolopyrrole (DPP) and thienopyrrolodione (TPD) moieties are investigated. The investigated series of polymers is obtained by varying the aromatic linker between the two acceptor motifs between thiophene, thiazole, pyridine, and benzene. High electron affinities between 3.96 and 4.42 eV, facilitated by the synergy of the acceptor motifs are determined with optical gaps between 1.37 and 2.02 eV. Grazing incidence wide‐angle X‐ray scattering studies reveal a range of film morphologies after thermal annealing, including face‐on, end‐on and superstructure edge‐on‐like crystallites. Conversely, all materials form thin edge‐on layers on the polymer–air interface, as demonstrated by multi‐elemental near‐edge X‐ray absorption fine‐structure spectroscopy. The benefit of the electron‐deficient linkers thiazole and pyridine is evident: In organic field effect transistors, electron mobilities of up to 4.6 × 10 −2 cm 2 V −1 s −1 are obtained with outstanding on/off current ratios of 5 × 10 5 , facilitated by the absence of detectable hole transport in these materials. Viability for all‐polymer solar cells is assessed in active layer blends with the donor polymer PM6, yielding a maximum average power conversion efficiency of 4.8% and an open circuit voltage above 1 V.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Photoenzymatic Hydrogenation of Heteroaromatic Olefins Using ‘Ene’‐Reductases with Photoredox Catalysts

Abstract Flavin‐dependent ‘ene’‐reductases (EREDs) are highly selective catalysts for the asymmetric reduction of activated alkenes. This function is, however, limited to enones, enoates, and nitroalkenes using the native hydride transfer mechanism. Here we demonstrate that EREDs can reduce vinyl pyridines when irradiated with visible light in the presence of a photoredox catalyst. Experimental evidence suggests the reaction proceeds via a radical mechanism where the vinyl pyridine is reduced to the corresponding neutral benzylic radical in solution. DFT calculations reveal this radical to be “dynamically stable”, suggesting it is sufficiently long‐lived to diffuse into the enzyme active site for stereoselective hydrogen atom transfer. This reduction mechanism is distinct from the native one, highlighting the opportunity to expand the synthetic capabilities of existing enzyme platforms by exploiting new mechanistic models.

Nakano, Yuji↗
DOE OSTI2017

Thermodynamic Stability of Heterodimetallic [LnLn'] Complexes: Synthesis and DFT Studies

The solid-state and solution configurations of the heterodimetallic complexes (Hpy)[LaEr(HL) 3 (NO 3 )(py)(H 2 O)] (1), (Hpy)[CeEr(HL) 3 (NO 3 )(py)(H 2 O)] (2), (Hpy)[CeGd(HL) 3 (NO 3 )(py)(H 2 O)] (3), (Hpy)[PrSm(HL) 3 (NO 3 )(py)(H 2 O)] (4), and (Hpy) 2 [LaYb(HL) 3 (NO 3 )(H 2 O)](NO 3 ) (5), in which H 3 L is 6-(3-oxo-3-(2-hydroxyphenyl)propionyl)pyridine-2-carboxylic acid and py is pyridine, were analyzed experimentally and by using DFT calculations. Complexes 3, 4, and 5 are described here for the first time, and were analyzed by using single-crystal X-ray diffraction and mass spectrometry. The theoretical study was also extended to the [LaCe] and [LaLu] analogues. The results are consistent with a remarkable selectivity of the metal distribution within the molecule in the solid state, enhanced by the size difference between the different ions. This selectivity was reduced in solution, particularly for ions with the most similar radii. This unique entry into 4f–4f" heterometallic chemistry establishes for the first time the difference between the selectivity in solution and that in the solid state, as a result of changes to the coordination that follow the dissociation of terminal ligands upon dissolution of the complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Reactivity of Silanes with ( tBu PONOP)Ruthenium Dichloride: Facile Synthesis of Chloro-Silyl Ruthenium Compounds and Formic Acid Decomposition

The coordination of tBu PONOP ( tBu PONOP=2,6-bis(ditert-butylphosphinito)pyridine) to different ruthenium starting materials, to generate ( tBu PONOP)RuCl 2 , was investigated in this paper. The resultant ( tBu PONOP)RuCl 2 reactivity with three different silanes was then investigated and contrasted dramatically with the reactivity of ( iPr PONOP)RuCl 2 (DMSO) ( iPr PONOP=2,6-bis(diisopropylphosphinito)pyridine) with the same silanes. The 16-electron species ( tBu PONOP)Ru(H)Cl was produced from the reaction of triethylsilane with ( tBu PONOP)RuCl 2 . Reactions of ( tBu PONOP)RuCl 2 with both phenylsilane or diphenylsilane afforded the 16-electron hydrido-silyl species ( tBu PONOP)Ru(H)(PhSiCl 2 ) and ( tBu PONOP)Ru(H)(Ph 2 SiCl), respectively. Reactions of all three of these complexes with silver triflate afforded the simple salt metathesis products of ( tBu PONOP)Ru(H)(OTf), ( tBu PONOP)Ru(H)(PhSiCl(OTf)), and ( tBu PONOP)Ru(H)(Ph 2 Si(OTf)). Formic acid dehydrogenation was performed in the presence of triethylamine (TEA), and each species proved competent for gas-pressure generation of CO 2 and H 2 . Finally, the hydride species ( tBu PONOP)Ru(H)Cl, ( tBu PONOP)Ru(H)(OTf), and ( tBu PONOP)Ru(H)(PhSiCl 2 ) exhibited faster catalytic activity than the other compounds tested.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States

The Ru complex [Ru II (bda-κ-N 2 O 2 )(N-NH 2 ) 2 ], 1, (bda 2- = (2,2'-bipyridine)-6,6'-dicarboxylate; N-NH 2 = 4-(pyridin-4-yl)aniline) is used as a synthetic intermediate to prepare Ru-bda complexes that contain the NO + , acetonitrile (MeCN) or H 2 O ligands at oxidation states II and III. Complex 1 reacts with excess NO + to form a Ru complex where the aryl amine ligands N-NH 2 in 1 are transformed into diazonium salts (N-N 2 + = 4-(pyridin-4-yl)benzenediazonium)) together with the formation of a new Ru-NO group at the equatorial zone, to generate [Ru II (bda-κ-N 2 O)(NO)(N-N 2 ) 2 ] 3+ , 2 3+ . Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature leading to complex [Ru II (bda-κ-N 2 O)(MeCN)(N-NH 2 ) 2 ], 3. Finally in acidic aqueous solutions solvent water coordinates the Ru center forming {[Ru II (bda-κ-(NO) 3 )(H 2 O)(N-NH 3 ) 2 ](H 2 O) n } 2+ , 4 2+ , that is strongly hydrogen bonded with additional water molecules at the second coordination sphere. We have additionally characterized the one electron oxidized complex {[Ru III (bda-κ-(NO) 3.5 )(H 2 O)(N-NH 3 ) 2 ](H 2 O) n } 3+ , 5 3+ . The coordination mode of the complexes has been studied both in the solid state and in solution through single-crystal XRD, X-ray absorption spectroscopy, variable-temperature NMR and DFT calculations. While the κ-N 2 O is the main coordination mode for 2 3+ and 3, an equilibrium that involves isomers with κ-N 2 O and κ-NO 2 coordination modes and neighboring hydrogen bonded water molecules is observed for 4 2+ and 5 3+ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Evidence of Alpha Radiolysis in the Formation of a Californium Nitrate Complex

Well-characterized complexes of transplutonium elements are scarce because of the experimental challenges of working with these elements and the rarity of the isotopes. This leads to a lack of structural and spectroscopic data needed to understand the nature of chemical bonds in these compounds. In this work, the synthesis of Cf(DOPO q ) 2 (NO 3 )(py) (DOPO q =2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate; py=pyridine) is reported, in which the nitrate anion is hypothesized to form through the α-radiolysis-induced reaction of pyridine and/or the ligand. Here, computational analysis of the electronic structure of the complex reveals that the Cf III –ligand interactions are largely ionic.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

C−H Activation of Inert Arenes using a Photochemically Activated Guanidinato‐Magnesium(I) Compound

Abstract UV irradiation of solutions of a guanidinate coordinated dimagnesium(I) compound, [{(Priso)Mg} 2 ] 3 (Priso=[(DipN) 2 CNPr i 2 ] − , Dip=2,6‐diisopropylphenyl), in either benzene, toluene, the three isomers of xylene, or mesitylene, leads to facile activation of an aromatic C−H bond of the solvent in all cases, and formation of aryl/hydride bridged magnesium(II) products, [{(Priso)Mg} 2 (μ‐H)(μ‐Ar)] 4 – 9 . In contrast to similar reactions reported for β‐diketiminate coordinated counterparts of 3 , these C−H activations proceed with little regioselectivity, though they are considerably faster. Reaction of 3 with an excess of the pyridine, p ‐NC 5 H 4 Bu t (py Bu t ), gave [(Priso)Mg(py Bu t H)(py Bu t ) 2 ] 10 , presumably via reduction of the pyridine to yield a radical intermediate, [(Priso)Mg(py Bu t ⋅)(py Bu t ) 2 ] 11 , which then abstracts a proton from the reaction solvent or a reactant. DFT calculations suggest two possible pathways to the observed arene C−H activations. One of these involves photochemical cleavage of the Mg−Mg bond of 3 , generating magnesium(I) doublet radicals, (Priso)Mg⋅. These then doubly reduce the arene substrate to give “Birch‐like” products, which subsequently rearrange via C−H activation of the arene. Circumstantial evidence for the photochemical generation of transient magnesium radical species includes the fact that irradiation of a cyclohexane solution of 3 leads to an intramolecular aliphatic C−H activation process and formation of an alkyl‐bridged magnesium(II) species, [{Mg(μ‐Priso −H )} 2 ] 12 . Furthermore, irradiation of a 1 : 1 mixture of 3 and the β‐diketiminato dimagnesium(I) compound, [{( Dip Nacnac)Mg} 2 ] ( Dip Nacnac=[HC(MeCNDip) 2 ] − ), effects a “scrambling” reaction, and the near quantitative formation of an unsymmetrical dimagnesium(I) compound, [(Priso)Mg−Mg( Dip Nacnac)] 13 . Finally, the EPR spectrum (77 K) of a glassed solution of UV irradiated 3 is dominated by a broad featureless signal, indicating the presence of a doublet radical species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Catalytic Enhancement of Inductively Heated Fe 3 O 4 Nanoparticles by Removal of Surface Ligands

Abstract Heat management in catalysis is limited by each material's heat transfer efficiencies, resulting in energy losses despite current thermal engineering strategies. In contrast, induction heating of magnetic nanoparticles (NPs) generates heat at the surface of the catalyst where the reaction occurs, reducing waste heat via dissipation. However, the synthesis of magnetic NPs with optimal heat generation requires interfacial ligands, such as oleic acid, which act as heat sinks. Surface treatments using tetramethylammonium hydroxide (TMAOH) or pyridine are used to remove these ligands before applications in hydrophilic media. In this study, Fe 3 O 4 NPs are surface treated to study the effect of induction heating on the catalytic oxidation of 1‐octanol. Whereas TMAOH was unsuccessful in removing oleic acid, pyridine treatment resulted in a roughly 2.5‐fold increase in heat generation and product yield. Therefore, efficient surfactant removal has profound implications in induction heating catalysis by increasing the heat transfer and available surface sites.

Moura, Natalia S.↗
DOE OSTI2021

Electrolysis on a Chip with Tunable Thin Film Nanostructured PGM Electrocatalysts Generated from Self-Assembled Block Copolymer Templates

Self-assembled block copolymers are promising templates for fabricating thin film materials with tuned periodic feature sizes and geometry at the nanoscale. Here, a series of nanostructured platinum and iridium oxide electrocatalysts templated from poly(styrene)-block-poly(vinyl pyridine) (PSbPVP) block copolymers via an incipient wetness impregnation (IWI) pathway is reported. Both nanowire and nanocylinder electrocatalysts of varying feature sizes are assessed and higher catalyst loadings are achieved by the alkylation of the pyridine moieties in the PVP block prior to IWI. Electrocatalyst evaluations featuring hydrogen pump and water electrolysis demonstrations are carried out on interdigitated electrode (IDE) chips flexible with liquid supporting electrolytes and thin film polymer electrolytes. Notably, the mass activities of the nanostructured electrocatalysts from alkylated block copolymer templates are 35%–94% higher than electrocatalysts from non-alkylated block copolymer templates. Standing cylinder nanostructures lead to higher mass activities than lamellar variants despite their not having the largest surface area per unit catalyst loading demonstrating that mesostructure architectures have a profound impact on reactivity. Overall, IDE chips with model thin film electrocatalysts prepared from self-assembled block copolymers offer a high-throughput experimental method for correlating electrocatalyst nanostructure and composition to electrochemical reactivity.

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

Synthesis and structure of lithium 3-trifluoromethyl-1,3-diketonates containing pyridyl substituents

Lithium 3-trifluoromethyl-1,3-diketonates containing pyridyl substituents were synthesized. The specific features of the crystal structures of lithium (Z)-1,1,1-trifluoro-4-oxo-4-(pyridin-3-yl)- and (Z)-1,1,1-trifluoro-4-oxo-4-(pyridin-4-yl)but-2-en-2-olates were revealed by X-ray diffraction. These compounds have a polymeric structure with lithium cations in different coordination modes. The 1,3-diketonate group is involved in chelation and formation of oxygen bridges, thereby linking two types of lithium atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Substituent Effects in the Pyridinium Catalyzed Reduction of CO 2 to Methanol: Further Mechanistic Insights

A series of substituted pyridiniums were examined for their catalytic ability to electrochemically reduce carbon dioxide to methanol. It is found that in general increased basicity of the nitrogen of the amine and higher LUMO energy of the pyridinium correlate with enhanced carbon dioxide reduction. The highest faradaic yield for methanol production at a platinum electrode was 39 ± 4 % for 4-aminopyridine compared to 22 ± 2 % for pyridine. However, 4-tertbutyl and 4-dimethylamino pyridine showed decreased catalytic behavior, contrary to the enhanced activity associated with the increased basicity and LUMO energy, and suggesting that steric effects also play a significant role in the behavior of pyridinium electrocatalysts. As a result, mechanistic models for the the reaction of the pyridinium with carbon dioxide are considered.

14 SOLAR ENERGY↗