A Spectroscopic and Computational Evaluation of Uranyl Oxo Engagement with Transition Metal Cations.

We report the synthesis and characterization of five novel Cd2+/UO22+ heterometallic complexes that feature Cd-oxo distances ranging from 78 to 171% of the sum of the van der Waals radii for these atoms. This work marks an extension of our previously reported Pb2+/UO22+ and Ag+/UO22+ complexes, yet with much more pronounced structural and spectroscopic effects resulting from Cd-oxo interactions. We observe a major shift in the U═O symmetric stretch and significant uranyl bond length asymmetry. The ρbcp values calculated using Quantum Theory of Atoms in Molecules (QTAIM) support the asymmetry displayed in the structural data and indicate a decrease in covalent character in U═O bonds with close Cd-oxo contacts, more so than in related compounds containing Pb2+ and Ag+. Second-order perturbation theory (SOPT) analysis reveals that O spx → Cd s is the most significant orbital overlap and U═O bonding and antibonding orbitals also contribute to the interaction (U═O σ/π → Cd d and Cd s → U═O σ/π*). The overall stabilization energies for these interactions were lower than those in previously reported Pb2+ cations, yet larger than related Ag+ compounds. Analysis of the equatorial coordination sphere of the Cd2+/UO22+ compounds (along with Pb2+/UO22+ complexes) reveals that 7-coordinate uranium favors closer, stronger Mn+-oxo contacts. These results indicate that U═O bond strength tuning is possible with judicious choice of metal cations for oxo interactions and equatorial ligand coordination.

Systematic Study of Solid-State U(VI) Photoreactivity: Long-Lived Radicalization and Electron Transfer in Uranyl Tetrachloride.

Reported are the syntheses, structural characterizations, and luminescence properties of three novel [UO2Cl4]2- bearing compounds containing substituted 1,1'-dialkyl-4,4'-bipyridinum dications (i.e., viologens). These compounds undergo photoinduced luminescence quenching upon exposure to UV radiation. This reactivity is concurrent with two phenomena: radicalization of the uranyl tetrachloride anion and photoelectron transfer to the viologen which constitutes the formal transfer of one electron from [UO2Cl4]2- to the viologen species. This behavior is elucidated using electron paramagnetic resonance (EPR) spectroscopy and further probed through a series of characterization and computational techniques including Rehm-Weller analysis, time-dependent density functional theory (TD-DFT), and density of states (DOS). This work provides a systematic study of the photoreactivity of the uranyl unit in the solid state, an under-described aspect of fundamental uranyl chemistry.

Structural, Spectroscopic, and Computational Analysis of Halogen- and Hydrogen-Bonding Effects within a Series of Uranyl Fluorides with 4-Halopyridinium.

Reported are the syntheses and characterization of five compounds containing one-dimensional uranyl fluoride chains charge balanced by 4-X-pyridinium (X = H, F, Cl, Br, I) cations. Structural analysis reveals molecular assembly via noncovalent interactions in the second coordination sphere with the X···Oyl interaction distances ranging from 2.987(7) to 3.142(3) Å, all of which are less than or close to the sum of the van der Waals radii. These interactions were probed via luminescence and Raman spectroscopy, where the latter indicates slight differences in the U═O symmetric stretches as a consequence of U═O in-phase and out-of-phase Raman-active stretches. The decrease in the X···Oyl sum of the van der Waals overlap between comparable compounds within the series manifests as a red-shifting trend among the Raman symmetric stretches. Computational density functional theory (DFT)-based frequency, electrostatic potential surfaces (ESPs), and natural bonding orbital (NBO) methods support the observed Raman spectroscopic features and provide a comprehensive rationale for assembly.

Orbital Engineering Mediated by Cation Conjugation in Luminescent Uranyl-Organic Hybrid Materials.

A series of compounds of the form [HAr]2 [UO2 X4 ] is reported here, wherein Ar is systematically varied between pyridine (1-X), quinoline (2-X), acridine (3-X), 2,5-dimethylpyrazine (4-X), quinoxaline (5-X), and phenazine (6-X), and X=Cl or Br. With greater conjugation in the organic cation, a larger quenching in uranyl luminescence is observed in the solid state. Supporting our luminescence experiments with computation, we map out the potential energy diagrams for the singlet and triplet states of both the [HAr]+ cations and [UO2 Cl4 ]2- anion in the crystalline state, and of the assembly. The distinct energy transfer pathways in each compound are discussed.

Bandgap modification in 0D tellurium iodide perovskite derivatives via incorporation of polyiodide species.

Halide perovskites provide a versatile platform for exploring the effect of non-covalent interactions, including halogen bonding, on material properties such as band gap, luminescence, and frontier orbital landscape. Herein we report six new zero-dimensional tellurium iodide perovskite derivatives, consisting of [TeI6]2- octahedra charge balanced by one of several X-Py cations (X = H, Cl, Br, I, and Py = pyridinium). These compounds also feature robust halogen bonding between [TeI6]2- octahedra and polyiodides in the form of I2 (1-4), I3 - (5), or adjacent octahedra (4 and 6). These relatively strong non-covalent interactions (NCIs) are modeled by natural bond order (NBO) and second order perturbation theory (SOPT) calculations. NCIs are responsible for reducing the bandgap of these materials (measured via diffuse reflectance spectroscopy) relative to those without polyiodide species. They also affect inner sphere bonding in the metal halide, exacerbating [TeI6]2- octahedron asymmetry as compared to previously published compounds, with greater asymmetry correlating with higher van der Waals overlap of halogen-halogen contacts. We also demonstrate the ability of hydrogen and carbon bonding (which dominates in the absence of polyiodides) to affect inner sphere tellurium iodide bonding and octahedral symmetry.

Plutonium Hybrid Materials: A Platform to Explore Assembly and Metal-Ligand Bonding.

We report the synthesis of five new hybrid materials containing the [PuCl6]2- anion and charge-balancing, noncovalent interaction donating 4-X-pyridinium (X = H, Cl, Br, I) cations. Single crystals of the title compounds were grown and harvested from acidic, chloride-rich, aqueous media, and their structures were determined via X-ray diffraction. Compounds 1-4, (4XPyH)2[PuCl6], and 5, (4IPyH)4[PuCl6]·2Cl, exhibit two distinct sheet-like structure types. Structurally relevant noncovalent interactions were tabulated from crystallographic data and verified computationally using electrostatic surface potential maps and the quantum theory of atoms in molecules (QTAIM). The strength of the hydrogen and halogen bonds was quantified using Kohn-Sham density functional theory, and a hierarchy of acceptor-donor pairings was established. The PuIV-Cl bonds were studied using QTAIM and natural localized molecular orbital (NLMO) analyses to delineate the underlying bond mechanism and hybrid atomic orbital contributions therein. The results of the PuIV-Cl bond analyses were compared across compositions via analogous treatments of previously reported [PuO2Cl4]2- and [PuCl3(H2O)5] molecular units. The Pu-Cl bonds are predominately ionic yet exhibit small varying degrees of covalent character that increases from [PuCl3(H2O)5] and [PuO2Cl4]2- to [PuCl6]2-, while the participation of the Pu-based s/d and f orbitals concurrently decreases and increases, respectively.

A novel symmetric pyrazine (pyz)-bridged uranyl dimer [UO2Cl3(H2O)(Pyz)0.5]22-: synthesis, structure and computational analysis.

Herein we report on the synthesis of (HPyz+)2[UO2Cl3(H2O)(Pyz)0.5]2·2H2O which features a novel pyrazine-bridged uranyl dimer, [UO2Cl3(H2O)(Pyz)0.5]22-. A rigorous computational and experimental analysis of this compound was performed to fully explore the influence of coordination on the electronic structure and potential charge-transfer characteristics of this dimer, revealing a delocalized π-system across the bridging pyrazine and the axial components of both uranyl centers. Electrostatic surface potentials, used to rationalize the observed assembly, indicate a decreased basicity of the uranyl oxo versus [UO2Cl4]2-, and signify a lessened capacity for the terminal -yl oxos of the [UO2Cl3(H2O)(Pyz)0.5]22- dimer to participate in supramolecular assembly. A combined density functional theory (DFT) and quantum theory of atoms in molecules (QTAIM) analysis further evidenced an increase in UO bond strengths within the dimer, which is supported by a blue shift in the characteristic Raman-active uranyl symmetric stretch (ν1) with respect to the more typically observed [UO2Cl4]2-.

A spectroscopic, structural, and computational study of Ag-oxo interactions in Ag+/UO22+ complexes.

Twelve novel Ag+/UO22+ heterometallic complexes have been prepared and characterized via structural, spectroscopic, and computational methods to probe the effects of Ag-oxo interactions on bonding and photophysical properties of the uranyl cation. Structural characterization reveals Ag-oxo interaction distances ranging from 2.475(3) Å to 4.287(4) Å. These interactions were probed using luminescence and Raman spectroscopy which displayed little effect on the luminescence intensity and the energy of the Raman active UO symmetric stretch peak as compared to previously reported Pb-oxo interactions. Computational efforts via density functional theory-based natural bond orbital analysis revealed that the highest stabilization energy associated with the Ag-oxo interaction had a value of only 11.03 kcal mol-1 and that all other energy values fell at 7.05 kcal mol-1 or below indicating weaker interactions relative to those previously reported for Pb2+/UO22+ heterometallic compounds. In contrast, quantum theory of atoms in molecules analysis of bond critical point electron density values indicated higher electron density in Ag-oxo interactions as compared to Pb-oxo interactions which suggests more covalent character with the Ag+. Overall, this data indicates that Ag+ has a less significant effect on UO22+ bonding and photophysical properties as compared to other Pb2+, likely due to the high polarizability of the cation.

Insight on noncovalent interactions and orbital constructs in low-dimensional antimony halide perovskites.

Reported is a series of eight antimony halide perovskite derivatives synthesized from acidic aqueous solutions of antimony oxide and halogen substituted pyridines. These materials feature anionic one-dimensional antimony halide (SbX; X = Cl, Br, I) chains or ribbons charge-balanced by organic para-halopyridinium cations (XPy; X = H, Cl, Br) which assemble into three-dimensional networks via halogen and hydrogen noncovalent interactions (NCIs) between ion pairs. Computational density functional theory (DFT) based natural bonding orbital (NBO) and density of state (DOS) methods were utilized to map the band structure and quantify and categorize noncovalent interaction strength and type. Moreover, we determined the presence of hybridized intermediate bands which are responsible for the small bandgap energies within this family and arise from mixing of the halide p-states and the Sb s-states. We note that the degree of hybridization, and thus optical properties, is influenced primarily by changes about inner sphere bonding and independent of second sphere interactions. This report is the first to specifically monitor the evolution of haloantimonate(III) hybrid perovskite atomic and molecular orbitals involved in optical behavior as a function of inner and outer sphere effects.

Pb-Oxo Interactions in Uranyl Hybrid Materials: A Combined Experimental and Computational Analysis of Bonding and Spectroscopic Properties.

Reported are the syntheses and characterization of six new heterometallic UO22+/Pb2+ compounds. These materials feature rare instances of M-oxo interactions, which influence the bonding properties of the uranyl cation. The spectroscopic effects of these interactions were measured using luminescence and Raman spectroscopy. Computational density functional theory-based natural bonding orbital and quantum theory of atoms in molecules methods indicate interactions arise predominantly through charge transfer between cationic units via the electron-donating uranyl O spx lone pair orbitals and electron-accepting Pb2+ p orbitals. The interaction strength varies as a function of Pb-oxo interaction distance and angle with energy values ranging from 0.47 kcal/mol in the longer contacts to 21.94 kcal/mol in the shorter contacts. Uranyl units with stronger interactions at the oxo display an asymmetric bond weakening and a loss of covalent character in the U═O bonds interacting closely with the Pb2+ ion. Luminescence quenching is observed in cases in which strong Pb-oxo interactions are present and is accompanied by red-shifting of the uranyl symmetric Raman stretch. Changes to inner sphere uranyl bonding manifest as a weakening of the U═O bond as a result of interaction with the Pb2+ ion. Comprehensive evaluation of the effects of metal ions on uranyl spectra supports modeling efforts probing uranyl bonding and may inform applications such as forensic signatures.

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln3+ Emission.

Reported are the syntheses, crystal structures, and photophysical properties of 28, novel lanthanide compounds across five structural types, [Ln(3-NO2Tp)2(NO3)] (1-Ln, Ln = La-Tm, except Pm), [Bu4N][Ln(3-NO2Tp)(NO3)3] (2-Ln, Ln = Yb, Lu), [Eu(3-NO2Tp)2Cl(H2O)]·2iPrOH (3-Eu), [{Ln(3-NO2Tp)2}2(µ2-CO3)]·MeOH (4-Ln, Ln = La-Gd, except Pm), and [{Ln(3-NO2Tp)}4(µ2-OMe)6(µ4-O)] (5-Ln, Ln = Pr-Tb, except Pm) with the 3-nitrotrispyrazolylborate (3-NO2Tp-) ligand. The reaction of methanol or isopropanol solutions of LnX3 (X = Cl, NO3) with the tetrabutyl ammonium salt of the flexidentate 3-NO2Tp- ([Bu4N][3-NO2Tp]) yields Ln(3-NO2Tp)x complexes of various nuclearities as either monomers (1-Ln, 2-Ln, 3-Eu), dimers (4-Ln), or tetramers (5-Ln) owing to the efficient conversion of atmospheric CO2 to CO32- (dimers) or ligand controlled solvolysis of lanthanide ions (tetramers). 3-NO2Tp- is an efficient sensitizer for both the visible and near-IR (NIR) emissions of most of the lanthanide series, except thulium. Optical measurements, supported by density functional theory calculations, indicate that the dual visible and NIR Ln3+ emission arises from two intraligand charge transfer (ILCT) transitions of 3-NO2Tp-. This is the first report of lanthanide complexes with a nitro-functionalized pyrazolylborate ligand. The derivatization of the known Tp- ligand results in new coordination chemistry governed by the increased denticity of 3-NO2Tp-, imparting remarkable structural diversity and charge transfer properties to resultant lanthanide complexes.

Bimetallic uranyl/cobalt(II) isothiocyanates: structure, property and spectroscopic analysis of homo- and heterometallic phases.

We report the synthesis and characterization of a family of UO22+/Co2+ isothiocyanate materials containing [UO2(NCS)5]3- and/or [Co(NCS)4]2- building units charged balanced by tetramethylammonium cations and assembled via SS or SOyl non-covalent interactions (NCIs), namely (C4H12N)3[UO2(NCS)5], (C4H12N)2[Co(NCS)4], and (C4H12N)5[Co(NCS)4][UO2(NCS)5]. The homometallic uranyl phase preferentially assembles via SS interactions, whereas in the heterometallic phase SOyl interactions are predominant. The variation in assembly mode is explored using electrostatic surfaces potentials, revealing that the pendant -NCS ligands of the [Co(NCS)4]2- anion is capable of outcompeting those of the [UO2(NCS)5]3- anion. Notably, the heterometallic phase displays atypical blue shifting of the uranyl symmetric stretch in the Raman spectra, which is in contrast to many other compounds featuring non-covalent interactions at uranyl oxygen atoms. A combined experimental and computational (density functional theory and natural bond orbital analyses) approach revealed that coupling of the uranyl symmetric stretch with isothiocyanate modes of equatorial -NCS ligands was responsible for the atypical blue shift in the heterometallic phase.

An Americium-Containing Metal-Organic Framework: A Platform for Studying Transplutonium Elements.

The synthesis, structure, and spectroscopic characterization of the first transplutonium metal-organic framework (MOF) is described. The preparation and structure of Am-GWMOF-6, [Am2 (C6 H8 O4 )3 (H2 O)2 ][(C10 H8 N2 )], is analogous to that of the isostructural trivalent lanthanide-only containing material GWMOF-6. The presented MOF architecture is used as a platform to probe Am3+ coordination chemistry and guest-enhanced luminescent emission, whereas the framework itself provides a means to monitor the effects of self-irradiation upon crystallinity over time. Presented here is a discussion of these properties and the opportunities that MOFs provide in the structural and spectroscopic study of actinides.

Novel Heterometallic Uranyl-Transition Metal Materials: Structure, Topology, and Solid State Photoluminescence Properties.

Six new uranyl hybrid materials have been synthesized solvothermally utilizing the ligands 2,2'-bipyridine-3,3'-dicarboxylic acid (H2L) and 2,2':6',2''-terpyridine (TPY). The six compounds are classified as either molecular complexes (I0O0 connectivity), [(UO2)(L)(TPY)]·H2O (1), [Ni(TPY)2][(UO2)(L)2]·3H2O (2), and [Cu(TPY)2][(UO2)(L)2]·3H2O (3), or 3D metal-organic frameworks (MOFs, I0O3 connectivity), [Cu2(UO2)2(OH)(C2H3O2)(L)3(TPY)2]·6H2O (4), [Zn2(UO2)2(OH)(NO3)(C2H3O2)(L)3(TPY)2]·4H2O (5), and Na[Ni(UO2)3(OH)(O)(L)3]·9H2O (6). A discussion of the influence of transition metal incorporation, chelating effects of the ligand, and synthesis conditions on the formation of uranyl materials is presented. The structure of compound 6 is of particular note due to large channel-like voids with a diameter of approximately 19.6 Å. A topological analysis of 6 reveals a new topology with a 9-nodal 3,3,3,3,3,3,3,4,5-connected network, designated geg1 hereafter. Further, solid state photoluminescence experiments show emission and lifetimes values consistent with related uranyl compounds.

A Thorium Metal-Organic Framework with Outstanding Thermal and Chemical Stability.

A new thorium metal-organic framework (MOF), Th(OBA)2 , where OBA is 4,4'-oxybis(benzoic) acid, has been synthesized hydrothermally in the presence of a range of nitrogen-donor coordination modulators. This Th-MOF, described herein as GWMOF-13, has been characterized by single-crystal and powder X-ray diffraction, as well as through a range of techniques including gas sorption, thermogravimetric analysis (TGA), solid-state UV/Vis and luminescence spectroscopy. Single-crystal X-ray diffraction analysis of GWMOF-13 reveals an interesting, high symmetry (cubic Ia 3 ‾ d) structure, which yields a novel srs-a topology. Most notably, TGA analysis of GWMOF-13 reveals framework stability to 525 °C, matching the thermal stability benchmarks of the UiO-66 series MOFs and zeolitic imidazolate frameworks (ZIFs), and setting a new standard for thermal stability in f-block based MOFs.

Life-history variation along environmental and harvest clines of a northern freshwater fish: Plasticity and adaptation.

Plasticity, local adaptation and evolutionary trade-offs drive clinal variation in traits associated with lifetime growth. Disentangling the processes and determinants that cause these traits to vary helps to understand species' responses to changing environments. This is particularly urgent for exploited populations, where size-selective harvest can induce life-history evolution. Lake trout (Salvelinus namaycush) are an exploited fish with a life history adapted to low-productivity freshwaters of northern North America, which makes them highly vulnerable to ecosystem changes and overfishing. We characterized life-history variation across a broad and diverse landscape for this iconic northern freshwater fish and evaluated whether clinal variation was consistent with hypotheses for local adaptation or growth plasticity. We estimated growth-associated traits for 90 populations exposed to a diversity of environments using a Bayesian multivariate hierarchical model. We tested for clinal variation in their somatic growth, size at maturity and reproductive allocation along environmental gradients of lake productivity, climate, prey and exploitation clines under competing hypotheses of plasticity and local adaptation. Clinal life-history variation was consistent with growth plasticity and local adaptations but not harvest-induced evolution. Variation in somatic growth was explained by exploitation, climate and prey fish occurrence. Increased exploitation, from pristine to fully exploited conditions, led to increased somatic growth (from 32 to 45 mm/year) and adult life spans, and reduced age at maturity (from 11 to 8 years). Variation in size at maturity was explained by climate and, less certainly, prey fish occurrence, while reproductive allocation was explained by evolutionary trade-offs with mortality and other traits, but not environment. Lake trout life-history variation within this range was as wide as that observed across dozens of other freshwater species. Lake trout life histories resulted from evolutionary trade-offs, growth plasticity and local adaptations along several environmental clines. Presuming a plastic response, we documented ~1.4-fold growth compensation to exploitation-lower growth compensation than observed in many freshwater fishes. These results suggest that harvested species exposed to spatially structured and diverse environments may have substantial clinal variation on different traits, but due to different processes, and this has implications for their resilience and successful management.

Plutonium chlorido nitrato complexes: ligand competition and computational metrics for assembly and bonding.

Four new [Pu(iv)Cln(NO3)6-n]2- (n = 0, 2, 3) and [Pu(vi)O2Cl3(NO3)]2- containing materials were crystallized from acidic, aqueous media and structurally characterized. The anions are assembled via hydrogen and halogen bonding motifs, which are rationalized computationally. The Pu-NO3 and -Cl bonds were probed using QTAIM and NLMO analyses and found to be polar and largely ionic.

Restricted Speciation and Supramolecular Assembly in the 5f Block.

Hybrid materials bearing elements from the 5f block display a rich diversity of coordination geometries, connectivities, and assembly motifs. Exemplary in this regard have been uranyl coordination polymers, which feature a wide range of secondary building units resulting from hydrolysis and oligomerization of the [UO2 ]2+ cation. An alternative approach to novel materials, however, suppresses hydrolysis and relies on non-covalent interactions (e.g. hydrogen or halogen bonding) to direct assembly of a more limited suite of species or building units. This may be achieved through the use of high-anion media to promote singular actinyl anions that are assembled with organic cations, or by way of functionalized chelating ligands that produce complexes suited for assembly through peripheral donor/acceptor sites. Presented in this Concept article is therefore an overview of our efforts in this arena. We highlight examples of each approach, share our thoughts regarding delineation of assembly criteria, and discuss the opportunities for exploring structure-property relationships in these systems.

How to Bend the Uranyl Cation via Crystal Engineering.

Bending the linear uranyl (UO22+) cation represents both a significant challenge and opportunity within the field of actinide hybrid materials. As part of related efforts to engage the nominally terminal oxo atoms of uranyl cation in noncovalent interactions, we synthesized a new uranyl complex, [UO2(C12H8N2)2(C7H2Cl3O2)2]·2H2O (complex 2), that featured both deviations from equatorial planarity and uranyl linearity from simple hydrothermal conditions. Based on this complex, we developed an approach to probe the nature and origin of uranyl bending within a family of hybrid materials, which was done via the synthesis of complexes 1-3 that display significant deviations from equatorial planarity and uranyl linearity (O-U-O bond angles between 162° and 164°) featuring 2,4,6-trihalobenzoic acid ligands (where Hal = F, Cl, and Br) and 1,10-phenanthroline, along with nine additional "nonbent" hybrid materials that either coformed with the "bent" complexes (4-6) or were prepared as part of complementary efforts to understand the mechanism(s) of uranyl bending (7-12). Complexes were characterized via single crystal X-ray diffraction and Raman, infrared (IR), and luminescence spectroscopy, as well as via quantum chemical calculations and density-based quantum theory of atoms in molecules (QTAIM) analysis. Looking comprehensively, these results are compared with the small library of bent uranyl complexes in the literature, and herein we computationally demonstrate the origin of uranyl bending and delineate the energetics behind this process.

Thermochromic Uranyl Isothiocyanates: Influencing Charge Transfer Bands with Supramolecular Structure.

The synthesis and structural characterization of seven new [UO2(NCS)5]3-- and [UO2(NCS)4Cl]3--containing materials charge balanced by 4-phenylpyridinium or 4,4'-bipyridinium cations are reported. Assembly of these materials occurs via a diverse set of noncovalent interactions, with the most prevalent involving the terminal sulfur atoms, which can both accept hydrogen bonds and/or form S···S and S···Oyl interactions. The electrostatic potential of the [UO2(NCS)5]3- and [UO2(NCS)4Cl]3- anions was calculated and mapped on the 0.001 au isodensity surface to rationalize the observed assembly modes and to provide an electrostatic basis to elucidate the role of the S atoms as both donors and acceptors of noncovalent interactions. Compounds 1-7 display a range of colors (red to yellow) as well as pronounced thermochromism. A computational treatment (time-dependent density functional theory, TDDFT) of the absorbance properties supports the temperature dependence on the ratio of inter- to intramolecular ligand to metal charge transfer (LMCT) bands as obtained from UV-vis diffuse reflectance analysis. Finally, the luminescence profiles of these materials feature additional peaks atypical for most uranyl-containing materials, and a combined spectroscopic (Raman, IR, and fluorescence) and computational (harmonic frequency calculations) effort assigns these as originating from vibronic coupling between the ν1 U═O symmetric stretch and bending modes of the isothiocyanate ligands.