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The furan ring-opening reaction using three catalytic models, HZSM-5, the extra-framework sites [GaO]/ZSM-5, and [Ga(OH)(2)]/ZSM-5, was investigated using periodic density functional theory as a model reaction for mechanistic understanding of catalytic vapor phase biomass upgrading. The formation of formyl allene from the furan was investigated in detail by computing the energy profiles and reaction barriers. Based on the computed free energy profiles, the HZSM-5 and [Ga(OH)(2)]/ZSM-5 are active catalysts, whereas [GaO]/ZSM-5 is not active for the furan ring-opening reaction. In HZSM-5, the likely rate-controlling step is furan CH2-O bond cleavage upon protonation (1.70 eV). The computed energy difference between the highest and lowest points in the free energy profile is 1.89 eV. The [Ga(OH)(2)](+) is likely the catalytic center for the gallium-incorporated ZSM-5 catalyst. The rate-controlling step is a hydrogen transfer reaction, which requires a reaction barrier of 2.48 eV. The computed energy difference between the highest and lowest points in the Ga(OH)(2) catalyzed free energy profile is 2.61 eV. These computational studies provide new mechanistic understanding of the role of catalytic extra-framework sites in the vapor phase upgrading reactions.
Widespread use of microwave technology requires quantitative scale-up models. Currently, microwave models are typical qualitative in nature. This work focuses on rendering models quantitative and elucidating the scale-up behavior of microwave heating using numerical simulations. A commonly used bench-scale microwave reactor from the CEM Corp. (CEM Discover SP) is used for benchmarking. To enable quantitative modeling, microwave heating experiments are conducted and compared to COMSOL calculations to develop a calibration curve for the set point vs the actually delivered microwave power. Using the validated computational model, microwave-heating of various liquids in a wide range of vial sizes is investigated. The computational study shows that during the scale-up, the volumetric power absorbed passes through a maximum, whereas the energy efficiency and heating uniformity exhibit strongly nonlinear behavior. As a result, this work introduces a method for quantitative microwave models and insights into the scale-up of commercial microwave reactors.
The separation of trivalent lanthanides and actinides is challenging because of their similar sizes and charge densities. S-donating extractants have shown significant selectivity for trivalent actinides over lanthanides, with single-stage americium/ lanthanide separation efficiencies for some thiol-based extractants reported at >99.999%. While such separations could transform the nuclear waste management landscape, these systems are often limited by the hydrolytic and radiolytic stability of the extractant. Progress away from thiol-based systems is limited by the poorly understood and complex interactions of these extractants in organic phases, where molecular aggregation and micelle formation obfuscates assessment of the metal–extractant coordination environment. Because S-donating thioethers are generally more resistant to hydrolysis and oxidation and the aqueous phase coordination chemistry is anticipated to lack complications brought on by micelle formation, we have considered three thioethers, 2,2'-thiodiacetic acid (TDA), (2R,5S)- tetrahydrothiophene-2,5-dicarboxylic acid, and 2,5-thiophenedicarboxylic acid (TPA), as possible trivalent actinide selective reagents. Formation constants, extended X-ray absorption fine structure spectroscopy, and computational studies were completed for thioether complexes with a variety of trivalent lanthanides and actinides including Nd, Eu, Tb, Am, Cm, Bk, and Cf. TPA was found to have moderately higher selectivity for the actinides because of its ability to bind actinides in a different manner than lanthanides, but the utility of TPA is limited by poor water solubility and high rigidity. While significant competition with water for the metal center limits the efficacy of aqueous-based thioethers for separations, the characterization of these solution-phase, S-containing lanthanide and actinide complexes is the most comprehensively available in the literature to date. Here, this is due to the breadth of lanthanides and actinides considered as well as the techniques deployed and serves as a platform for the further development of Scontaining reagents for actinide separations. Additionally, this paper reports on the first bond lengths for Cf and Bk with a neutral S donor.
We report the use of the reported Fe-phthalocyanine complex, PcFe (1; Pc = 1,4,8,11,15,18,22,25-octaethoxy-phthalocyanine), to generate PcFe–amine complexes 1-(NH 3 ) 2 , 1-(MeNH 2 ) 2 , and 1-(Me 2 NH) 2 . Treatment of 1 or 1-(NH 3 ) 2 to an excess of the stable aryloxide radical, 2,4,6-tritert-butylphenoxyl radical ( t Bu ArO•), under NH 3 resulted in catalytic H atom abstraction (HAA) and C–N coupling to generate the product 4-amino-2,4,6-tritert-butylcyclohexa-2,5-dien-1-one (2) and t Bu ArOH. Exposing 1-(NH 3 ) 2 to an excess of the trityl (CPh 3 ) variant, 2,6-di-tert-butyl-4-tritylphenoxyl radical ( Tr ArO • ), under NH 3 did not lead to catalytic ammonia oxidation as previously reported in a related Ru-porphyrin complex. However, pronounced coordination-induced bond weakening of both α N–H and β C–H in the alkylamine congeners, 1-(MeNH 2 ) 2 and 1-(Me 2 NH) 2 , led to multiple HAA events yielding the unsaturated cyanide complex, 1-(MeNH 2 )(CN), and imine complex, 1-(MeN=CH 2 ) 2 , respectively. Subsequent C–N bond formation was also observed in the latter upon addition of a coordinating ligand. Detailed computational studies support an alternating mechanism involving sequential N–H and C–H HAA to generate these unsaturated products.
The activation of small molecules via multielectron redox processes offers promise in mediating difficult transformations related to energy conversion processes. While molecular systems that engage in one- and two-electron redox processes are widespread, those that participate in the direct transfer of four or more electrons to small molecules are very rare. To that end, we report a mononuclear Cr II complex competent for the 4-electron reduction of dioxygen (O 2 ) and nitrosoarenes. These systems additionally engage in facile two-electron group transfer reactivity, including O atom excision and nitrene transfer. Structural, spectroscopic, and computational studies support bond activation processes that intimately occur at a mononuclear chromium(phosphinimide) center and highlight the unusual structural responsiveness of the phosphinimides in stabilizing a range of metal redox states.
A family of 8- and 9- coordinate homoleptic dimethyl sulfoxide An(IV) complexes is used to evaluate the solvation properties of tetravalent actinide ions in dimethyl sulfoxide (DMSO) vs aqueous media. These compounds are prepared from aqueous mixtures of DMSO and yield crystalline solids, whose solid-state electronic absorption spectra are compared to solution phase spectra, providing insight into the solution speciation. The thermodynamics of the equilibria between the 8- and 9-coordinate compounds were determined experimentally and computationally, showing a trend that correlates with ionic radius. Cyclic voltammetry data for the +IV/+III couples of Np and Pu in the DMSO electrolyte indicate that the +IV ions are significantly stabilized compared to aqueous media due to the more donating nature of DMSO compared to water. As a result, computational studies of these systems indicate that further reactivity may take place upon reduction to the +III oxidation state.
A new icosahedral quasicrystalline phase, CaAu 4.5–x Al 1.5+x [0.11 ≤ x ≤ 0.40(6); CaAu 4.4 Al 1.6 , a QC = 5.383(4) Å, and Pm35], and its lowest-order 1/0 cubic crystalline approximant phase, CaAu 3+x Al 1–x [0 ≤ x ≤ 0.31(1); a = 9.0766(5)–9.1261(8) Å, Pa3(No. 205), and Pearson symbol cP40], have been discovered in the Ca-poor region of the Ca–Au–Al system. In the crystalline approximant, eight [Au 3–x Al 1+x ] tetrahedra fill the unit cell, and each tetrahedron is surrounded by four Ca atoms, thus forming a three-dimensional network of {Ca 4/4 [Au 3–x Al 1+x ]} tetrahedral stars. Here, a computational study of Au and Al site preferences concurs with the experimental results, which indicate a preference for near-neighbor Au–Al interactions over Au–Au and Al–Al interactions. Analysis of the electronic density of states and the associated crystal orbital Hamilton population curves was used to rationalize the descriptions of CaAu 4.5–x Al 1.5+x [0.11 ≤ x ≤ 0.46(6)] and CaAu 3+x Al 1–x [0 ≤ x ≤ 0.31(1)] as polar intermetallic species, whereby Ca atoms engage in polar covalent bonding with the electronegative, electron-deficient [Au 3–x Al 1+x ] tetrahedral clusters and the observed phase width of the crystalline approximant.
Here, Pt-based heterobimetallic lantern complexes of the form [PtM(SOCR) 4 (L)] have been shown previously to form intermolecular metallophilic interactions and engage in antiferromagnetic coupling between lanterns having M atoms with open shell configurations. In order to understand better the influence of the carboxylate bridge and terminal ligand on the electronic structure, as well as the metal–metal interactions within each lantern unit, a series of diamagnetic lantern complexes, [PtMg(SAc) 4 (OH 2 )] (1), [PtMg(tba) 4 (OH 2 )] (2), [PtCa(tba) 4 (OH 2 )] (3), [PtZn(tba) 4 (OH 2 )] (4), and a mononuclear control (Ph 4 P) 2 [Pt(SAc) 4 ] (5) have been synthesized. Crystallographic data show close Pt–M contacts enforced by the lantern structure in each dinuclear case. 195 Pt-NMR spectroscopy of 1–4, (Ph 4 P) 2 [Pt(SAc) 4 ] (5), and several previously reported lanterns revealed a strong chemical shift dependence on the identity of the second metal (M), mild influence by the thiocarboxylate ligand (SOCR; R = CH 3 (thioacetate, SAc), C 6 H 5 (thiobenzoate, tba)), and modest influence from the terminal ligand (L). Fluorescence spectroscopy has provided evidence for a Pt···Zn metallophilic interaction in [PtZn(SAc) 4 (OH 2 )], and computational studies demonstrate significant dative character. In all of 1–4, the short Pt–M distances suggest that metal-only Lewis donor (Pt)–Lewis acceptor (M) interactions could be present. DFT and NBO calculations, however, show that only the Zn examples have appreciable covalent character, whereas the Mg and Ca complexes are much more ionic.
Not much is known about the crystal chemistry of neptunyl peroxide compounds compared to uranyl peroxide compounds, for which dozens of structures have been described. Uranyl peroxides are formed over a broad range of pH and solution conditions, but neptunyl peroxide chemistry is complicated by the ability of H 2 O 2 to act as an oxidizing or reducing agent for Np, depending on the conditions present. The combination of Np(V) in 1 M HCl, H 2 O 2 , and CaCl 2 under alkaline conditions leads to the immediate crystallization of a neptunyl triperoxide monomer, Ca 2 [NpO 2 (O 2 ) 3 ]·9H 2 O, which is the first Np(VI)-based peroxide compound to be characterized in the solid state and is isostructural to Ca 2 [UO 2 (O 2 ) 3 ]·9H 2 O. The crystal structure reveals bond distances of 1.842(7) Å that are the longest reported to date for nonbridging Np(VI)-O yl bonds. Computational studies probe the oxidation state and bond distances of the monomer unit and differences in Raman spectra of the neptunyl and uranyl triperoxide compounds.
Metastable materials are abundant in nature and technology, showcasing remarkable properties that inspire innovative materials design. However, traditional crystal structure prediction methods, which rely solely on energetic factors to determine a structure’s fitness, are not suitable for predicting the vast number of potentially synthesizable phases that represent a local minimum corresponding to a state in thermodynamic equilibrium. Here, we present a new approach for the prediction of metastable phases with specific structural features, and interface this method with the XTALOPT evolutionary algorithm. Our method relies on structural features that include the local crystalline order (e.g., the coordination number or chemical environment), and symmetry (e.g., Bravais lattice and space group) to filter the breeding pool of an evolutionary crystal structure search. The effectiveness of this approach is benchmarked on three known metastable systems: XeN 8 , with a two-dimensional polymeric nitrogen sublattice, brookite TiO 2 , and a high pressure BaH 4 phase that was recently characterized. Additionally, a newly predicted metastable melaminate salt, P1¯WC 3 N 6 , was found to possess an energy that is lower than two phases proposed in a recent computational study. Here, the method presented here could help in identifying the structures of compounds that have already been synthesized, and developing new synthesis targets with desired properties.
Eleven conjoined coumarins possessing a chromeno[3,4-c]chromene-6,7-dione skeleton have been synthesized via the reaction of electron-rich phenols with esters of coumarin-3-carboxylic acids, catalyzed by either Lewis acids or 4-dimethylaminopyridine. Furthermore, Michael-type addition to angular benzo[f]coumarins is possible, leading to conjugated helical systems. Arrangement of the electron-donating amino groups at diverse positions on this heterocyclic skeleton makes it possible to obtain π-expanded coumarins with emission either sensitive to, or entirely independent of, solvent polarity with large Stokes shifts. Computational studies have provided a rationale for moderate solvatochromic effects unveiling the lack of collinearity of the dipole moments in the ground and excited states. Depending on the functional groups present, the obtained dyes are highly polarized with dipole moments of ~14 D in the ground state and ~20–25 D in the excited state. Strong emission in nonpolar solvents, in spite of the inclusion of a NO 2 group, is rationalized by the fact that the intramolecular charge transfer introduced into these molecules is strong enough to suppress intersystem crossing yet weak enough to prevent the formation of dark twisted intramolecular charge transfer states. Photochemical transformation of the dye possessing a chromeno[3,4-c]pyridine-4,5-dione scaffold led to the formation of a spirocyclic benzo[g]coumarin.
A combined anion photoelectron spectroscopic and relativistic electronic-structure computational study of the electronic structure of the UN 2 molecule is reported. Since the photoelectron spectrum of uranium dinitride’s negative ion, UN 2 - , (UN 2 plus an additional electron) directly reflects the electronic structure of neutral UN 2 , we have measured and relied upon the photoelectron spectrum of the UN 2 – anion as a means of mapping the electronic structure of neutral UN 2 . In addition to the electron affinity of the UN 2 ground state (the energy released when attaching an electron to UN 2 molecule), energy levels of the UN 2 excited states (electronic states with higher energies than the ground state) were well characterized by the close interplay between experiment and high-level theory. We found that both electron attachment and electronic excitation significantly bend the UN 2 molecule and elongate its U≡N bond. Implications for the activation of UN 2 are discussed.
Density functional theory (DFT) and coupled cluster theory (CCSD(T)) were used to research the addition of CO 2 to group 4 (MO 2 ) n and group 6 (MO 3 ) n (n = 1, 2, 3) nanoclusters. The structures and energetics arising from Lewis acid–base addition (physisorption) and formation of CO 3 2– (chemisorption) of CO 2 to these clusters were predicted. Physisorption and chemisorption of CO 2 are predicted to be thermodynamically allowed for group 4 (MO 2 ) n clusters, with chemisorption being more favored energetically. Correlations of the ligand binding energies (LBEs) for the group 4 clusters are made with the fluoride affinities and M–O and M=O bond strengths of the clusters. The LBEs for chemisorption on the Zr and Ti clusters are consistent with published experimental and computational studies of bulk solids. Physisorption LBEs for the Ti and Zr clusters are more exothermic than the bulk values, as the cluster models allow for better relaxation at the metal sites. Chemisorption is not predicted to occur with group 6 (MO 3 ) n clusters, as the larger chemisorbed structures were all found to be metastable. Furthermore, CO 2 is predicted to weakly physisorb to (WO 3 ) n with physisorption correlating with the Lewis acidity of the metal site.
We perform a theoretical and computational study of relativistic one-electron homonuclear diatomic quasimolecules subject to strong electromagnetic fields linearly polarized along the molecular axis. Several quasimolecules with the nuclear charges 1 to 92 and appropriately scaled internuclear distances and field parameters are used in the calculations. The time-dependent Dirac equation is solved with the help of the generalized pseudospectral method in prolate spheroidal coordinates. We have found that employing this coordinate system makes it possible to avoid emergence of spurious states, which usually show up when solving the Dirac equation numerically. For lower carrier frequencies, interaction with the driving field is described within the dipole approximation. Relativistic effects in the multiphoton ionization probabilities are investigated with respect to the internuclear distance in the quasimolecule. In conclusion, for higher frequencies, the interaction with the field is described beyond the dipole approximation. Nondipole effects in the ionization probability are discussed.
The aldol reaction catalyzed by an amine-substituted mesoporous silica nanoparticle (amine-MSN) surface was investigated using a large molecular cluster model (Si 392 O 958 C 6 NH 361 ) combined with the surface integrated molecular orbital/molecular mechanics (SIMOMM) and fragment molecular orbital (FMO) methods. Three distinct pathways for the carbinolamine formation, the first step of the amine-catalyzed aldol reaction, are proposed and investigated in order to elucidate the role of the silanol environment on the catalytic capability of the amine-MSN material. Here the computational study reveals that the most likely mechanism involves the silanol groups actively participating in the reaction, forming and breaking covalent bonds in the carbinolamine step. Furthermore, the active participation of MSN silanol groups in the reaction mechanism leads to a significant reduction in the overall energy barrier for the carbinolamine formation. In addition, a comparison between the findings using a minimal cluster model and the Si 392 O 958 C 6 NH 361 cluster suggests that the use of larger models is important when heterogeneous catalysis problems are the target.
We have synthesized and characterized a family of zwitterionic liquids (ZwLs) based on the poly(ethylene oxide) imidazolium cation and the alkyl sulfonate anion. To better rationalize ZwLs′ structural behavior and networkforming properties, we have computationally studied them in contrast to isostructural but chemically untethered ionic liquid (IL) analogues. Perhaps surprisingly, it is the molecular liquids and not the ILs that show the most selfassembly and intermediate-range order associated with scattering prepeaks; the ZwLs display also the slowest dynamics. This is consistent with prior work showing the importance of networks in considering the viscoelastic relaxation of liquids. We find that, because of their significantly large molecular dipoles, these zwitterions are versatile network-building blocks that result in highly viscous liquids. From a structural perspective, networks in these ZwLs sit somewhere in between what would be true chemical connectivity and the Coulombic networks observed in ionic liquids.
Light harvesting 2 (LH2) complex is the primary component of the photosynthetic unit of purple bacteria that is responsible for harvesting and relaying excitons. The electronic absorption line shape of LH2 contains two major bands at 800 and 850 nm wavelength regions. Under low light conditions, some species of purple bacteria replace LH2 with light harvesting 3 (LH3), a variant form with almost the same structure as the former but with distinctively different spectral features. The major difference between the absorption line shapes of LH2 and LH3 is the shift of the 850 nm band of the former to a new 820 nm region. The microscopic origin of this difference has been the subject of some theoretical/computational investigations. However, the genuine molecular level source of such a difference is not clearly understood yet. This work reports a comprehensive computational study of LH2 and LH3 complexes so as to clarify different molecular level features of LH2 and LH3 complexes and to construct simple exciton-bath models with a common form. All-atomistic molecular dynamics simulations of both LH2 and LH3 complexes provide detailed molecular level structural differences of bacteriochlorophylls (BChls) in the two complexes, in particular, in their patterns of hydrogen bonding (HB) and torsional angles of the acetyl group. Time-dependent density functional theory calculation of the excitation energies of BChls for structures sampled from the MD simulations suggests that the observed differences in the HB and torsional angles cannot fully account for the experimentally observed spectral shift of LH3. Potential sources that can explain the actual spectral shift of LH3 are discussed, and their magnitudes are assessed through fitting of experimental line shapes. Furthermore, these results demonstrate the feasibility of developing simple exciton-bath models for both LH2 and LH3, which can be employed for large-scale exciton quantum dynamics in their aggregates.