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At least 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Single Molecule Junctions: A Laboratory for Chemistry, Mechanics and Bond Rupture

Simultaneous measurement [1] of junction conductance and sustained force in single molecule junctions bridging metal electrodes provides a powerful tool in the quantitative study of the character of molecule-metal bonds. In this talk I will discuss three topics. First, I will describe chemical trends in link bond strength based on experiments and Density Functional Theory based calculations. Second, I will focus on the specific case of pyridine-linked junctions. Bond rupture from the high conductance junction structure shows a requires a force that exceeds the rupture force of gold point contacts and clearly indicates the role of additional forces, beyond the specific N-Au donor acceptor bond. DFT-D2 calculations with empirical addition of dispersion interactions illustrates the interplay between the donor-acceptor bonding and the non-specific van der Waals interactions between the pyridine rings and Au asperities. Third, I will describe recent efforts to characterize the diversity of junction structures realized in break-junction experiments with suitable models for the potential surfaces that are observed. [1] Venkataraman Group, Columbia University.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Characterization of an explosively bonded aluminum proton beam window for the Spallation Neutron Source

An effort is underway at the Spallation Neutron Source (SNS) to change the design of the 1st Generation high-nickel alloy proton beam window (PBW) to one that utilizes aluminum for the window material. One of the key challenges to implementation of an aluminum PBW at the SNS was selection of an appropriate joining method to bond an aluminum window to the stainless steel bulk shielding of the PBW assembly. An explosively formed bond was selected as the most promising joining method for the aluminum PBW design. A testing campaign was conducted to evaluate the strength and efficacy of explosively formed bonds that were produced using two different interlayer materials: niobium and titanium. The characterization methods reported here include tensile testing, thermal-shock leak testing, optical microscopy, and advanced scanning electron microscopy. All tensile specimens examined failed in the aluminum interlayer and measured tensile strengths were all slightly greater than the native properties of the aluminum interlayer, while elongation values were all slightly lower. A leak developed in the test vessel with a niobium interlayer joint after repeated thermal-shock cycles, and was attributed to an extensive crack network that formed in a layer of niobium-rich intermetallics located on the bond interfaces of the niobium interlayer; the test vessel with a titanium interlayer did not develop a leak under the conditions tested. Due to the experience gained from these characterizations, the explosively formed bond with a titanium interlayer was selected for the aluminum PBW design at the SNS.

316L Stainless Steel↗
DOE OSTI2022

Diffusion bonded compact heat exchanger in Inconel 740H for high temperature and high-pressure applications

It is desired to develop heat exchangers able to be operated at high temperatures (750˚C) and pressures (3636 psi) for use in advanced Brayton power cycle. Conventional materials have not had the high strength at temperature required for these applications previously, however a fairly new material Inconel 740H developed by Special Metals for the ultra-supercritical water fossil industry has shown good performance under these conditions. In further efforts to capitalize on these new high strength high temperature alloys CompRex has developed a diffusion bonding procedure capable of alloying compact high effectiveness heat exchangers that can perform under these high temperature and high-pressure conditions. Initial tests of the heat exchanger are being conducted at the University of Wisconsin using supercritical CO2 working fluid. The bonding process has been adjusted such that the strength of the bonded block has achieved over 90% yield and tensile strength of the 740H base material values. Grain size before and after bonding were measured to determine the extent of grain growth and grain diffusion across the interface. A discussion of the heat exchanger design, etching and initial tensile tests on sample bonds will be discussed.

14 SOLAR ENERGY↗
DOE OSTI2015

Propane σ‐Complexes on PdO(101): Spectroscopic Evidence of the Selective Coordination and Activation of Primary CH Bonds

Abstract Achieving selective CH bond cleavage is critical for developing catalytic processes that transform small alkanes to value‐added products. The present study clarifies the molecular‐level origin for an exceptionally strong preference for propane to dissociate on the crystalline PdO(101) surface via primary CH bond cleavage. Using reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations, we show that adsorbed propane σ‐complexes preferentially adopt geometries on PdO(101) in which only primary CH bonds datively interact with the surface Pd atoms at low propane coverages and are thus activated under typical catalytic reaction conditions. We show that a propane molecule achieves maximum stability on PdO(101) by adopting a bidentate geometry in which a HPd dative bond forms at each CH 3 group. These results demonstrate that structural registry between the molecule and surface can strongly influence the selectivity of a metal oxide surface in activating alkane CH bonds.

Zhang, Feng↗
DOE OSTI2021

New Noncentrosymmetric Tetrel Pnictides Composed of Square‐Planar Gold(I) with Peculiar Bonding

Abstract Three novel isostructural equiatomic gold tetrel pnictides, AuSiAs, AuGeP, and AuGeAs, were synthesized and characterized. These phases crystallize in the noncentrosymmetric (NCS) monoclinic space group Cc (no. 9), featuring square‐planar Au within cis ‐[AuTt 2 Pn 2 ] units (Tt=tetrel, Si, Ge; Pn=pnictogen, P, As). This is in drastic contrast to the structure of previously reported AuSiP, which exhibits typical linear coordination of Au with Si and P. Chemical bonding analysis through the electron localization function suggests covalent two‐center two‐electron Tt−Pn bonds, and three‐center Au−Tt−Au and Au−Pn−Au bonds with 1.6 e − per bond. X‐ray photoelectron spectroscopy studies support the covalent and nonionic nature of Au−Pn and Au−Tt bonds. The title materials were found to be n ‐type narrow‐gap semiconductors or semimetals, with nearly temperature‐independent electrical resistivities and low thermal conductivities. A combination of the semimetallic properties with tunable NCS structure provides opportunities for the development of materials based on gold tetrel pnictides.

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

Chapter One - Selectivity in the activation of C–H bonds by rhodium and iridium complexes

Trispyrazolylborate complexes of rhodium and iridium have been extensively investigated over the past 3 decades with special attention to their ability to activate C–H bonds. The rhodium complexes of tris-(3,5-dimethylpyrazolyl)borate have been the subject of numerous thermodynamic investigations that provide information about rhodium-metal carbon bond strengths. This insight arises as a result of the reversibility of C–H activation with rhodium. In the case of iridium, C–H bond activation reactions are also widespread, and some of these also show reversibility. Access to some key trispyrazolylborate iridium(I) and iridium(III) starting materials has given way to a multitude of studies of reactions with small molecules in which C–H bonds are made and broken reversibly. The stability of Fischer carbenes plays a role in the observed products. Here, the reactivity of trispyrazolylborate complexes of rhodium and iridium compounds over the past decade (since 2010) are summarized here. Related reactions of X–H bonds with these trispyrazolylborate compounds are also included for completeness (X = O, N, S, B, Si).

02 PETROLEUM↗
DOE OSTI2014

Mechanisms of selective cleavage of C–O bonds in di-aryl ethers in aqueous phase

A novel route for cleaving the C-O aryl ether bonds of p-substituted H-, CH 3 -, and OH- diphenyl ethers has been explored over Ni/SiO 2 catalysts at very mild conditions. The C-O bond of diphenyl ether is cleaved by parallel hydrogenolysis and hydrolysis (hydrogenolysis combined with HO* addition) on Ni. The rates as a function of H 2 pressure from 0 to 10 MPa indicate that the rate-determining step is the C-O bond cleavage on Ni. H* atoms compete with the organic reactant for adsorption leading to a maximum in the rate with increasing H 2 pressure. In contrast to diphenyl ether, hydrogenolysis is the exclusive route for cleaving an ether C-O bond of di-p-tolyl ether to form p-cresol and toluene. 4,4'-dihydroxydiphenyl ether undergoes sequential surface hydrogenolysis, first to phenol and HOC 6 H 4 O* (adsorbed), which is then cleaved to phenol (C 6 H 5 O* with added H*) and H 2 O (O* with two added H*) in a second step. Density function theory supports the operation of this pathway. Notably, addition of H* to HOC 6 H 4 O* is less favorable than a further hydrogenolytic C-O bond cleavage. The TOFs of three aryl ethers with Ni/SiO 2 in water followed the order 4,4'-dihydroxydiphenyl ether (69 h -1 ) > diphenyl ether (26 h -1 ) > di-p-tolyl ether (1.3 h -1 ), in line with the increasing apparent activation energies, ranging from 93 kJ∙mol -1 (4,4'-dihydroxydiphenyl ether) < diphenyl ether (98 kJ∙mol -1 ) to di-p-tolyl ether (105 kJ∙mol -1 ). D.M. thanks the support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.

Aqueous phase reaction↗
DOE OSTI2018

Additive manufacturing of anisotropic hybrid NdFeB-SmFeN nylon composite bonded magnets

In this work, we demonstrate a novel method of extrusion-based 3D printing additive manufacturing of bonded magnets comprising 65 vol% anisotropic composite powders of Dy-free magfine Nd-Fe-B and Sm-Fe-N in nylon. The 3D printing was performed using a big area additive manufacturing (BAAM) process. The effects of various post-printing alignment with different magnetic field intensities and temperatures on the properties of the anisotropic bonded Nd-Fe-B + Sm-Fe-N composite magnets were investigated. Remanence increases with alignment magnetic field leading to an increase in energy product, (BH) max . For anisotropic Nd-Fe-B + Sm-Fe-N composite bonded magnets with a 65 vol% loading fraction, (BH) max of up to 11.3 MGOe are obtained. In addition, the magnetic properties of the bonded magnets can be tuned through the post-printing alignment of anisotropic particles in different directions without impairing the original shape-changing effect. Finally, this technique shows great promise for producing anisotropic bonded magnets with enhanced magnetic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

A series of six coordination compounds ([Zn(5-Brnic){sub 2}]·1.5H{sub 2}O){sub n} (1), [Cd(5-Brnic){sub 2}]{sub n} (2), [Co(5-Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (3), [Zn(5-Brnic){sub 2}(H{sub 2}biim)]{sub n} (4), ([Cd(5-Brnic){sub 2}(phen)]·H{sub 2}O){sub n} (5), and [Pb(5-Brnic){sub 2}(phen)] (6) have been generated by the hydrothermal method from the metal(II) nitrates, 5-bromonicotinic acid (5-BrnicH), and an optional ancillary 1,10-phenanthroline (phen) or 2,2′-biimidazole (H{sub 2}biim) ligand. All the products 1–6 have been characterized by IR spectroscopy, elemental, thermal, powder and single-crystal X-ray diffraction analyses. Their 5-bromonicotinate-driven structures vary from the 3D metal-organic framework with the seh-3,5-P21/c topology (in 2) and the 2D interdigitated layers with the sql topology (in 1 and 3), to the 1D chains (in 4 and 5) and the 0D discrete monomers (in 6). The 5-bromonicotinate moiety acts as a versatile building block and its tethered bromine atom plays a key role in reinforcing and extending the structures into diverse 3D supramolecular networks via the various halogen bonding Br⋯O, Br⋯Br, and Br⋯π interactions, as well as the N–H⋯O and C–H⋯O hydrogen bonds. The obtained results demonstrate a useful guideline toward engineering the supramolecular architectures in the coordination network assembly under the influence of various halogen bonding interactions. The luminescent (for 1, 2, 4, 5, and 6) and magnetic (for 3) properties have also been studied and discussed in detail. - Graphical abstract: Six coordination compounds driven by 5-bromonicotinic acid have been generated and structurally characterized, revealing diverse metal-organic networks that are further reinforced and extended via various halogen bonding interactions. - Highlights: • 5-Bromonicotinic acid is a versatile ligand for Zn, Cd, Co and Pb derivatives. • Careful selection of co-ligands and metals resulted in different network structures. • Halogen and hydrogen bonding interactions lead to various supramolecular networks. • Luminescent and magnetic properties were studied and discussed in detail.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Layered vanadyl (IV) nitroprusside: Magnetic interaction through a network of hydrogen bonds

The hydrogen bond and π-π stacking are two non-covalent interactions able to support cooperative magnetic ordering between paramagnetic centers. This contribution reports the crystal structure and related magnetic properties for VO[Fe(CN){sub 5}NO]·2H{sub 2}O, which has a layered structure. This solid crystallizes with an orthorhombic unit cell, in the Pna2{sub 1} space group, with cell parameters a=14.1804(2), b=10.4935(1), c=7.1722(8) Å and four molecules per unit cell (Z=4). Its crystal structure was solved and refined from powder X-ray diffraction data. Neighboring layers remain linked through a network of hydrogen bonds involving a water molecule coordinated to the axial position for the V atom and the unbridged axial NO and CN ligands. An uncoordinated water molecule is found forming a triple bridge between these last two ligands and the coordinated water molecule. The magnetic measurements, recorded down to 2 K, shows a ferromagnetic interaction between V atoms located at neighboring layers, with a Curie-Weiss constant of 3.14 K. Such ferromagnetic behavior was interpreted as resulting from a superexchange interaction through the network of strong OH····O{sub H2O}, OH····N{sub CN}, and OH····O{sub NO} hydrogen bonds that connects neighboring layers. The interaction within the layer must be of antiferromagnetic nature and it was detected close to 2 K. - Graphical abstract: Coordination environment for the metals in vanadyl (II) nitroprusside dihydrate. Display Omitted - Highlights: • Crystal structure of vanadyl nitroprusside dehydrate. • Network of hydrogen bonds. • Magnetic interactions through a network of hydrogen bonds. • Layered transition metal nitroprussides.

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

Microstructural evolution and micromechanical properties of gamma-irradiated Au ball bonds

The effect of gamma radiation on the mechanical and structural properties of gold ball bonds was investigated. Gold wires from thermosonic wire bonding were exposed to gamma rays from a Cobalt-60 source at a low dose (5 Gy). The load–depth curve of nanoindentation for the irradiated gold wire bond has an apparent staircase shape during loading compared to the as-received sample. The hardness of the specimens calculated from the nanoindentation shows an increase in value from 0.91 to 1.09 GPa for specimens after exposure. The reduced elastic modulus for irradiated specimens significantly increased as well, with values from 75.18 to 98.55 GPa. The change in intrinsic properties due to gamma radiation was investigated using dual-focused ion beam and high-resolution transmission electron microscope analysis. The dual-focused ion beam and high-resolution transmission electron microscope images confirmed the changes in grain structure and the presence of dislocations. The scanning electron microscope micrographs of focused ion beam cross sections showed that the grain structure of the gold became elongated and smaller after exposure to gamma rays. Meanwhile, high-resolution transmission electron microscopy provided evidence that gamma radiation induced dislocation of the atomic arrangement. - Highlights: • Nanoindentation technique provides a detailed characterisation of Au ball bond. • P–h curve of irradiated Au ball bond shows an apparent pop-in event. • Hardness and reduced modulus increased after exposure. • Elongated and smaller grain structure in irradiated specimens • Prevalent presence of dislocations in the atomic arrangement.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Study of mechanical joint strength of aluminum alloy 7075-T6 and dual phase steel 980 welded by friction bit joining and weld-bonding under corrosion medium

We have employed a unique solid-sate joining process, called friction bit joining (FBJ), to spot weld aluminum alloy (AA) 7075-T6 and dual phase (DP) 980 steel. Static joint strength was studied in the lap shear tension configuration. In addition, weld-bonding (adhesive + FBJ) joints were studied in order to evaluate the ability of adhesive to mitigate the impact of corrosion on joint properties. Accelerated laboratory cyclic corrosion tests were carried out for both FBJ only and weld-bonding joints. Furthermore, the FBJ only joints that emerged from corrosion testing had lap shear failure loads that were significantly lower than freshly prepared joints. However, weld-bonding specimens retained more than 80% of the lap shear failure load of the freshly prepared weld-bonding specimens. Moreover, examination of joint cross sections confirmed that the presence of adhesive in the weld-bonding joints mitigated the effect of the corrosion environment, compared to FBJ only joints.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Creep performance of transient liquid phase bonded haynes 230 alloy

In this study, creep performance of a potential heat exchanger alloy, Haynes 230 was investigated. To simulate mechanical performance of a heat exchanger, sheet material of Haynes 230 transient liquid phase (TLP) bonded together. Sheets were plated on both sides with a Ni–P compound, subsequently stacked and TLP bonded together. Duplicate creep tests show low scatter in creep results, meaning a good repeatable joint was formed by TLP bonding. Overall creep performance showed less ductility and shorter times to failure than specimens originating from plate material. Lastly, evolution of a phosphorous compound at the bond line was observed and thought to potentially reduce ductility of the TLP bonded alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Fabrication and Design Aspects of High-Temperature Compact Diffusion Bonded Heat Exchangers

The Very High Temperature Reactor (VHTR) using gas-cooled reactor technology is anticipated to be the reactor type for the Next Generation Nuclear Plant (NGNP). In this reactor concept with an indirect power cycle system, a high-temperature and high integrity Intermediate Heat Exchanger (IHX) with high effectiveness is required to efficiently transfer the core thermal output to a secondary fluid for electricity generation, hydrogen production, and/or industrial process heat applications. At present, there is no proven IHX concept for VHTRs. The current Technology Readiness Level (TRL) status issued by NGNP to all components associated with the IHX for reduced nominal reactor outlet temperatures of 750–800 degrees C is 3 on a 1–10 scale, with 10 indicating omplete technological maturity. Among the various potential IHX concepts available, diffusion bonded heat exchangers (henceforth called printed circuit heat exchangers, or PCHEs) appear promising for NGNP applications. The design and fabrication of this key component of NGNP with Alloy 617, a candidate high-temperature structural material for NGNP applications, are the primary focus of this paper. In the current study, diffusion bonding of Alloy 617 has been demonstrated, although the optimum diffusion bonding process parameters to engineer a quasi interface-free joint are yet to be determined. The PCHE fabrication related processes, i.e., photochemical etching and diffusion bonding are discussed for Alloy 617 plates. In addition, the authors’ experiences with these non-conventional machining and joining techniques are discussed. Two PCHEs are fabricated using Alloy 617 plates and are being experimentally investigated for their thermal-hydraulic performance in a High-Temperature Helium Facility (HTHF). The HTHF is primarily of Alloy 800H construction and is designed to facilitate experiments at temperatures and pressures up to 800 degrees C and 3 MPa, respectively. Furthermore, some preliminary microstructural and mechanical property characterization studies of representative diffusion bonded Alloy 617 specimens are presented. The characterization studies are restricted and less severe from an NGNP perspective but provide sufficient confidence to ensure safe operation of the heat exchangers in the HTHF. The test results are used to determine the design operating conditions for the PCHEs fabricated.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2020

Hydrogen-Bonded Organic Frameworks: A Rising Class of Porous Molecular Materials

Hydrogen-bonded organic frameworks (HOFs) are a class of porous molecular materials that rely on the assembly of organic building blocks by means of hydrogen-bonding interactions to form two-dimensional (2D) and three-dimensional (3D) crystalline networks. The reversible nature of the hydrogen-bond formation endows HOFs with the attributes of solution processability and simple regeneration. High-quality single crystals of HOFs can be grown easily for unambiguous superstructure determination by single-crystal X-ray diffraction, which is crucial for the elucidation of superstructure–property relationships. During the past decade, considerable progress has been achieved in realizing stable HOFs with permanent porosities by focusing on the design of molecular building blocks in order to introduce rigidity, auxiliary [π···π] interactions, and interpenetration of their frameworks to sustain the extended networks. The applications of HOFs are far-reaching, spanning catalysis, energy, and biomedical products as well as the storage and separation of fine chemicals. In this paper, we, first of all, provide an overview of the chronological development of HOFs, starting from the seminal work by Marsh and Duchamp in 1969 on the crystal superstructure of the hydrogen-bonded networks of trimesic acid. We identify the development of novel hydrogen-bonding motifs such as diaminotriazine (DTA), the introduction of the concept of molecular tectonics, and the establishment of permanent porosity in HOFs as being some of the milestones, which incentivized the current burgeoning research endeavors on developing HOFs as multifunctional materials. This Account is focused primarily on surveying the strategies for constructing porous 3D HOFs based on organic building blocks with peripheral carboxyl groups. These strategies are presented in the following categories: (1) the polycatenation of 2D networks by trigonal building blocks to form global 3D frameworks, (2) the utilization of building blocks with 3D geometries—tetrahedral and trigonal prismatic—that are predisposed to form 3D networks, and (3) the docking by shape-fitting of geometrically labile building blocks. We emphasize how the molecular geometry of the building blocks plays an important role in modulating the superstructures of extended frameworks so as to address specific applications. Recognizing that the in silico design of HOFs is the ultimate goal of researchers in this field, we also discuss the recent advances in superstructure prediction that lead to the formation of porous supramolecular crystals and assess the complications in implementing computational methods for HOFs with complex superstructures. We hope this Account will inspire the development of new supramolecular designs and creative approaches to crystal engineering that aid and abet the assembly of multifunctional HOFs with customizable properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Tuning the Mechanical Properties of a Polymer Semiconductor by Modulating Hydrogen Bonding Interactions

Conjugation breakers (CBs) with different H-bonding chemistry and linker flexibility are designed and incorporated into a Diketopyrrolopyrrole (DPP)-based conjugated polymer backbone. The effects of H-bonding interactions on polymer semiconductor morphology, mechanical properties and electrical performance are systematically investigated. We observe that CBs with H-bonding self-association constant >0.7 or denser packing tendency are able to induce higher polymer chain aggregation and crystallinity in as-casted thin film, resulting in higher modulus and crack on-set strain. Additionally, the rDoC (relative degree of crystallinity) of the stretched thin film with the highest crack on-set strain only suffers a small decrease, suggesting the main energy dissipation mechanism is the breakage of H-bonding interactions. By contrast, other less stretchable polymer films dissipate strain energy through the breakage of crystalline domains, indicated by drastic decrease in rDoC. Furthermore, we evaluate their electrical performance under mechanical strain in fully stretchable field-effect transistors. The polymer with the highest crack on-set strain has the least degradation in mobility as a function of strain. Overall, these observations suggest that we can aptly tune the mechanical properties in polymer semiconductors by modulating intermolecular interactions, such as H-bonding chemistry and linker flexibility. Such understanding provides molecular design guidelines for future stretchable semiconductors.

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

Americium Oxalate: An Experimental and Computational Investigation of Metal–Ligand Bonding

A novel actinide-containing coordination polymer, [Am(C 2 O 4 )(H 2 O) 3 Cl] (Am-1), has been synthesized and structurally characterized. The crystallographic analysis reveals that the structure is two-dimensional and comprised of pseudo-dimeric Am 3+ nodes that are bridged by oxalate ligands to form sheets. Each metal center is nine-coordinate, forming a distorted capped square antiprism geometry with a C 1 symmetry, and features bound oxalate, aqua, and chloro ligands. The Am 3+ –ligand bonds were probed computationally using the quantum theory of atoms in molecules nd natural localized molecular orbital approaches to investigate the underlying mechanisms and hybrid atomic orbital contributions therein. The analyses indicate that the bonds within Am-1 are predominantly ionic and the 5f shell of the Am 3+ metal centers does not add a significant covalent contribution to the bonds. Further, our bonding assessment is supported by measurements on the optical properties of Am-1 using diffuse reflectance and photoluminescence spectroscopies. The position of the principal absorption band at 507 nm ( 5 L 6' ← 7 F 0' ) is notable because it is consistent with previously reported americium oxalate complexes in solution, indicating similarities in the electronic structure and ionic bonding. Compound Am-1 is an active phosphor, featuring strong bright-blue oxalate-based luminescence with no evidence of metal-centered emission.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Uranyl Naphthylsalophen and Pyrasal Complexes: Oxo Ligands Acting as Hydrogen Bond Acceptors in the Solid State

Uranium is most stable when it is exposed to oxygen or water in its +6 oxidation state as the uranyl (UO 2 2+ ) ion. This ion is subsequently particularly stable and very resistant to functionalization due to the inverse trans effect. Uranyl oxo ligands are typically not considered good hydrogen bond acceptors due to their weak Lewis basicity; however, the ligands bound in the equatorial plane greatly affect the strength of the oxo ligands’ hydrogen bonding. Here, in this work, new naphthylsalophen and pyrasal complexes of uranium were synthesized and crystallized for characterization in the solid state. The bond lengths and angles of the uranyl ion and the ligand conformation are compared. In the solid state, one of the pyrasal complexes showed a hydrogen bond directly from a water molecule to the uranyl oxo ligand, which resulted in an asymmetric lengthening of the U–O yl bonds from 1.789 to 1.862 Å and 1.784 to 1.844 Å.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗