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This investigation elucidates the special role of Al in these hetero-binuclear compounds, providing new insights into the peculiar electronic structure of aluminyls, which may help for the rational control of their unprecedented reactivity toward carbon dioxide. The syntheses and photophysical characterization of five new gold I complexes bearing diphenylamine-substituted fluorenyl moieties are reported; four are characterized by X-ray diffraction crystallography.
Ancillary ligation on gold I is provided by organophosphine and N-heterocyclic carbene ligands. All of these chromophores are dual luminescent in a toluene solution at K. The alkynyl derivative containing a phosphine ancillary ligand, Au-ADPA0, is a white-light emitter, while the alkynyl derivative containing an N-heterocyclic carbene ancillary ligand, Au-ADPA1, is a yellow-light emitter. Spin-restricted density functional theory calculations support the assignments of ligand-centric optical transitions but with contributions of ligand-to-metal charge transfer involving the vacant Au 6p orbital.
The single-crystal-to-single-crystal SCSC transformations of metal—organic frameworks MOFs are fascinating because we can directly observe the change of the crystal structure during the transformation process. It also greatly helps to understand the delicate interaction between the guest molecules and the skeleton framework and therefore fosters a deep understanding of gas storage and separation within the frameworks.
Although the structure and coordination patterns of compound 1 are pretty different from those of 2, the two Cu-MOFs were prepared from identical ligands and similar reaction conditions. Interestingly, compound 1 will change to 2 wholly and gradually after the addition of a certain amount of Py with a small amount of dilute hydrochloric acid. Furthermore, both compounds 1 and 2 could be used as excellent heterogeneous catalysts toward the cyanosilylation reaction under solvent-free conditions.
Complex 1Aq has been further characterized by X-ray crystallography. A comparative study of the water oxidation activity catalyzed by 1Aq and 2Aq is reported here to see the effect of a dangling carboxylic group in the catalytic performance. Complex 2Aq shows an enormously higher rate of reaction than 1Aq. The present work provides experimental evidence of the uncommon functionality of the carboxylic group, the oxide relay, in molecular water oxidation chemistry.
Controlling the structure of halide perovskites through component engineering, and thus revealing the changes in luminescence properties caused by the conversion of crystal structure, is of great significance.
Meanwhile, the relationship between perovskite structure and luminescence mechanism has been systematically revealed. These environmentally stable halide perovskites have great potential to be applied in optoelectronic devices. The compounds 1c, 2c, 4c, and 5c absorb UV light only, whereas compound 3c absorbs in the visible-light region of the solar spectrum. The as-prepared cubic bismuth III -based oxides 1c—5c were studied with regard to the photocatalytic decomposition of rhodamine B under visible-light irradiation with compound 3c showing the highest turnover and efficiency.
Efforts are also made to evaluate the impact of temperature variation on the sensitization efficiency. Current research provides a practical guideline for analyzing the luminescence sensitization effect in the donor—acceptor system, which facilitates the development of materials with unique optical features. Mechanistic studies on 1,2-azaphospholene formation showed the reductive elimination of LiCl to form a phosphonium salt that readily adds one of the P—C bonds oxidatively to the in situ generated Pt0 species to form a chelate complex 3.
The quenching constants of NFAs and fluoroquinolones range from 0. It also shows a luminescent response to real antibiotic drugs containing NFAs and fluoroquinolones. Herein, we report coupling in situ high temperature postsynthetic modifications PSMs in metal—organic frameworks MOFs. The major oxidative process was thermolysis of the chromene ring with a minor pathway of allylic-type oxidation to give heterocyclic chromenone functionality.
All transformations were fully compatible with the requirements to maintain MOF crystallinity and porosity as evidenced by surface area analysis and X-ray powder diffraction measurements. The exchangeable counterions in ionic metal—organic frameworks IMOFs provide facile and versatile handles to manipulate functions associated with the ionic guests themselves and host—guest interactions.
However, anion-exchangeable stable IMOFs combining multiple anion-related functions are still undeveloped. In this work, a novel porous IMOF featuring unique self-penetration was constructed from an electron-deficient tris pyridinium -tricarboxylate zwitterionic ligand.
The water-stable IMOF undergoes reversible and single-crystal-to-single-crystal anion exchange and shows selective and discriminative ionochromic behaviors toward electron-rich anions owing to donor—acceptor interactions. The IMOFs with different anions are good ionic conductors with low activation energy, the highest conductivity being observed with chloride. Furthermore, integrating Lewis acidic sites and nucleophilic guest anions in solid state, the IMOFs act as heterogeneous and recyclable catalysts to efficiently catalyze the cycloaddition of CO2 to epoxides without needing the use of halide cocatalysts.
The catalytic activity is strongly dependent upon the guest anions, and the iodide shows the highest activity. The results demonstrate the great potential of developing IMOFs with various functions related to the guest ions included in the porous matrices.
To facilitate the transition of nanozymes from benchtop to real-world applications, we herein present a one-step approach, which only needs mixing of two broad commercialized reagents at room temperature, to harvest gold nanoparticles—bovine serum albumin BSA nanocomposite BSA-Au with distinct oxidase-like activity and good stability in a broad range of harsh conditions.
Density functional theory DFT calculations demonstrate the oxidase-like activity of BSA-Au stemming from thermodynamically and kinetically favored facets for O2 activation. The reactive oxygen species ROS generation of BSA-Au contributes to the catalytic activities and further enables water sterilization and antibacterial applications against superbugs.
This one-step strategy promises great potential in bulk production of nanozyme for broad application beyond laboratory use. The fully dehydrated form was obtained using an environmental gas cell technique in a stepwise manner followed by its CO2-pressurized structure at K using in situ crystallography.
Two-dimensional 2D metal—organic framework MOF nanosheets, with largely exposed surface area and highly accessible active sites, have emerged as a novel kind of sensing material.
Given the great threat posed to the ecological environment by anti-inflammatory drugs and pesticides, the developed luminescent Zn-MOF nanosheets were utilized to determine these organic pollutants, achieving highly selective and sensitive detection of diclofenac sodium DCF and tetramethylthiuram disulfide TMTD. The remarkable quenching performance for DCF and TMTD stems from a combined effect of photoinduced electron transfer and competitive energy absorption.
The possible sensing mechanism was systematically investigated by the studies of powder X-ray diffraction, UV—vis, luminescence lifetime, and density functional theory calculations. A half-conjugate polydentate Salamo—Salen hybrid ligand, H5L, containing two unique N2O2 pockets was first designed so that these metal ions in the complexes appear in different coordination modes. IR spectral analysis of the two complexes showed the existence of monodentate- and bidentate-coordinated acetate ions.
The fluorescence properties of the ligand and its two heterohexanuclear complexes were explored in MeOH and water solutions, separately. In addition, theoretical calculations density functional theory, interaction region indicator, and bond order were performed to further understand the formation of a single-molecular double helix and the electron distribution characteristics of the two complexes.
The development of heterogeneous, chemoselective, and tandem catalytic systems using abundant metals is vital for the sustainable synthesis of fine and commodity chemicals. We report a robust and recyclable single-site cobalt-hydride catalyst based on a porous aluminum metal—organic framework DUT-5 MOF for chemoselective hydrogenation of arenes.
The DUT-5 node-supported cobalt II hydride DUTCoH is a versatile solid catalyst for chemoselective hydrogenation of a range of nonpolar and polar arenes, including heteroarenes such as pyridines, quinolines, isoquinolines, indoles, and furans to afford cycloalkanes and saturated heterocycles in excellent yields.
DUTCoH exhibited excellent functional group tolerance and could be reusable at least five times without decreased activity. The same MOF-Co catalyst was also efficient for tandem hydrogenation—hydrodeoxygenation of aryl carbonyl compounds, including biomass-derived platform molecules such as furfural and hydroxymethylfurfural to cycloalkanes.
In the case of hydrogenation of cumene, our spectroscopic, kinetic, and density functional theory DFT studies suggest the insertion of a trisubstituted alkene intermediate into the Co—H bond occurring in the turnover limiting step. Our work highlights the potential of MOF-supported single-site base—metal catalysts for sustainable and environment-friendly industrial production of chemicals and biofuels.
Estimates of the potential at pH 12 were consistent with extrapolating that line to high pH. These results show that the common surface-charging explanation of the pH dependence is not tenable in these systems. Oxidation of reduced c-TiO2R with the electron-transfer oxidant potassium triiodide KI3 occurred with a significant drop in pH, showing that protons were released when the electrons were removed from the NPs. Maintaining a long-term continuous and stable reactivator blood concentration to treat organophosphorus nerve agent poisoning using acetylcholinesterase AChE reactivator pralidoxime chloride 2-PAM is very important yet difficult.
This was because the composite showed different swelling behaviors in different solvents. For mice after intragastric poisoning with sarin a neurotoxic agent , an atropine-assisted [email protected] Fe treatment experiment revealed that [email protected] Fe continuously released 2-PAM for more than 72 h so that poisoned AChE was continuously and steadily reactivated.
The reactivation rate of AChE was This composite is expected to provide a prolonged, stable therapeutic drug for the mid- and late-stage treatment of neurotoxic agent poisoning. Nanocubic MoS2—FeS2, as a photocatalyst, was synthesized with high catalytic active edges and high specific surface areas with the capability of absorbing visible light.
The adsorption process was found to follow a kinetic model of a pseudo-second-order kind Qe. The photodegradation process was achieved by holes. This extractant can be directly compared to the recently studied saturated hexathiacrown-6 HT18C6. The default conformation of the S lone pairs in UHT18C6 is endodentate, where the pocket of the charge density, according to the crystal structures, is oriented toward the center of the ring, which should allow better extraction for Hg II compared to the exodentate HT18C6.
Batch study experiments showed that Hg II had better extraction at low acid molarity ca. Speciation studies were conducted with the goal of delineating a plausible extraction mechanism. Density functional theory calculations including relativistic effects were carried out on both Hg II -encapsulated HT18C6 and UHT18C6 complexes to shed light on the binding strength and the nature of bonding. Our calculations offer insights into the extraction mechanism.
Finally, the extraction kinetics were explored to assess whether this crown can extract the short-lived Cn II species in a future online experiment. The conversion of peroxide to hydroxyl occurs through interaction of neighboring lattice H2O molecules and ionization of the peroxide O—O bond, which produces two hydroxyls, and allows isolation of the important monomer building block, UO2 O2 2 OH 24—, that is ubiquitous in uranyl capsule polyoxometalates.
Steric crowding in the equatorial plane of the uranyl ion develops and promotes transformation to an amorphous phase. We disclose herein an efficient regioselective B 3,4 —H activation via a ligand strategy, affording B 3 -monoacyloxylated and B 3,4 -diacyloxylated o-carboranes. The identification of amino acid and phosphoric acid ligands is crucial for the success of B 3 -mono- and B 3,4 -diacyloxylation, respectively. This ligand approach is compatible with a broad range of carboxylic acids.
The functionalization of complex drug molecules is demonstrated. Other acyloxyl sources, including sodium benzoate, benzoic anhydride, and iodobenzene diacetate, are also tolerated.
Magnetic susceptibility, specific heat, dielectric, and electric polarization of LiCuFe2 VO4 3 have been investigated. Although a dielectric peak at TN1 is clearly identified, the measured pyroelectric current also exhibits a sharp peak at TN1, implying the magnetically relevant ferroelectricity.
Interestingly, another pyroelectric peak around TN2 with an opposite signal is observed, resulting in the disappearance of electric polarization below TN2.
Besides, the electric polarization is significantly suppressed in response to external magnetic field, evidencing a remarkable magnetoelectric effect. These results suggest the essential relevance of the magnetic structure with the ferroelectricity in LiCuFe2 VO4 3, deserving further investigation of the underlying mechanism.
The nonahydridorhenate dianion ReH92— is a unique rhenium polyhydride complex due to its remarkably high coordination number; however, its detailed polytopal rearrangement process in either solution or crystal is so far unclear. In this work, our quantum chemical calculations have identified two previously unreported fluxional mechanisms for the ReH92— dianion in the K2ReH9 crystal: three-arm turnstile rotation and circle dance mechanism. These two polytopal rearrangements in the crystal offer an alternative interpretation to the pulse and wide-line NMR spectra Farrar et al.
However, for Au2F2 with a zigzag conformation, the d10—d10 closed-shell interaction between the AuF monomers is demonstrated as a coordinate covalent bond. Based on our study, one of the 5d orbitals of the Au atom is activated to hybridize with its 6s and 6p orbitals to form hybridized dsp2 orbitals, where each Au atom is both an electron donor Lewis base and acceptor Lewis Acid in dimerization.
Nonlinear optical NLO materials are playing an increasingly vital role in laser science and technology. In contrast, polarization from the anionic group and the volume of the unit cell are reduced. This research provides a viable strategy for the design and synthesis of new NLO crystals. This phenomenon could arise from the different cationic radii and lattice parameters of ZnS and MnS.
These findings contribute to the rational synthesis of novel 1D semiconductor heteronanostructures with multicomponents and benefit the development of optoelectronic devices. Mixing iodide and perchloric acid solutions with an excess of chlorate inside a diode-array spectrophotometer led to the observation of an abrupt decrease of the absorbance at the nm isosbestic point after an induction period.
The clock time decreases by increasing the initial concentrations of chlorate and acid, but increasing the initial iodide concentration has an opposite effect.
The proposed mechanism simulates the experimental results and considers the interaction of UV light with iodide, producing iodine and triiodide ion. A chelator that effectively binds and retains these radionuclides is required for this application.
The development of ligands for this purpose, however, is challenging because the large ionic radii and charge-diffuse nature of these metal ions give rise to weaker metal—ligand interactions. There has been considerable research interest in the ligand nature of N-heterocyclic carbenes NHCs. Single-crystal X-ray characterizations demonstrate that both complexes have strongly ruffled conformations and relatively perpendicular ligand orientations which are forced by the sterically bulky 1,3-Me2Imd NHC ligands.
Multitemperature 4. They were successfully synthesized by a UV light-induced one-pot reaction where TTF oxidation and formation of MCl63— occurred sequentially. According to the cyclic voltammograms CV and electron spin resonance ESR spectra, increased conductivity is because of the higher degree of back charge transfer from MCl63— in TTF3InCl6 compared to TTF3SbCl6, which is due to the lower electronegativity of In, considering that the only difference between the two compounds is the center metal.
Herein we describe the synthesis and characterization of several multimetal cluster complexes that contain this unit. Magnetometry indicated a strong antiferromagnetic interaction between paramagnetic centers in 6 and 7. The ability of 4 and 6—8 to form linkage isomers and release NO upon irradiation in the solid state was investigated by IR spectroscopy.
The electronic structure of 6 was also studied by an X-ray charge density analysis. The current approach was convenient and clean, and only 0.
The easy work-up procedure, gram-scale synthesis, usage of nontoxic solvent, improved yield, short reaction times, and high durability of the catalyst are several remarkable advantages of the current approach.
Photodriven oxidations of alkanes in trifluoroacetic acid using commercial and synthesized Fe III sources as catalyst precursors and dioxygen O2 as the terminal oxidant are reported. The reactions produce alkyl esters and occur at ambient temperature in the presence of air, and catalytic turnover is observed for the oxidation of methane in a pure O2 atmosphere.
It is demonstrated that methyl trifluoroacetate is stable under catalytic conditions, and thus overoxidized products are not formed through secondary oxidation of methyl trifluoroacetate. Detection of oxygen though color change is highly desirable for rapid qualitative analysis like the case of pH test papers. This work demonstrates 3O2-assisted photoinduced color change of a new photochromic coordination compound [Zn 4-aminopyridine 2Cl2] ZnaPyCl , which represents the first photochromic compound with a selective 3O2 detection ability.
The compound underwent photoinduced intraligand charge separation and formed a stable diradical-like triplet species in the solid state or in frozen solution, accompanied by conversion of triplet oxygen to singlet oxygen.
However, it is essential to understand how the shell thickness affects interfacial charge separation. This work explores the impact of shell thickness on photoinduced electron transfer PET and photoinduced hole transfer PHT with an electron acceptor benzoquinone and a hole acceptor phenothiazine, respectively. These results highlight the impact of shell thickness on the excited-state interactions of green-emitting g-QDs and conclude that g-QDs with a relatively thin shell can be a better choice as photoactive materials for photocatalyst, photodetector, and solar cells.
The immobilization of molecularly precise metal complexes to substrates, such as silica, provides an attractive platform for the design of active sites in heterogeneous catalysts. Specific steric and electronic variations of the ligand environment enable the development of structure—activity relationships and the knowledge-driven design of catalysts.
At present, however, the three-dimensional environment of the precatalyst, much less the active site, is generally not known for heterogeneous single-site catalysts.
We explored the degree to which NMR-based surface-to-complex interatomic distances could be used to solve the three-dimensional structures of three silica-supported metal complexes. The structure solution revealed unexpected features related to the environment around the metal that would be difficult to discern otherwise.
This approach appears to be highly robust and, due to its simplicity, is readily applied to most single-site catalysts with little extra effort. Magnetite, Fe3O4, is the oldest known magnetic mineral and archetypal mixed-valence oxide. Despite its recognized role in deep Earth processes, the behavior of magnetite at extreme high-pressure high-temperature HPHT conditions remains insufficiently studied.
The latter has never been predicted for iron compounds. Our experiments demonstrate that HPHT conditions promote the formation of ferric-rich Fe—O compounds, thus arguing for the possible involvement of magnetite in the deep oxygen cycle.
Further, the reductive dechlorination converting RhIRhIII 4b,d to RhI2 1b,d was accomplished with a CO terminal ligand by reacting with various amines that acted as one-electron reducing agents through an inner-sphere electron transfer mechanism.
DFT calculations were performed to elucidate the electronic structures of 1a—d and 4a—d and to estimate the structures of the hydride intermediate complexes 2 and 3. Understanding the mechanisms governing temperature-dependent magnetic resonance properties is essential for enabling thermometry via magnetic resonance imaging. Solution-phase Raman spectroscopy in the low-frequency — cm—1 regime reveals a red shift of Raman-active Co—N6 vibrational modes by deuteration.
A simple and facile synthetic pathway for accessing new derivatizable bulky-demanding octahydrofluorenyl OHF ligands has been developed, and a series of half-sandwich rare-earth metal Sc, Y, Lu complexes bearing the OHF ancillary ligands have been synthesized.
The design and preparation of efficient and low-cost catalysts for water electrolysis are crucial and highly desirable to produce eco-friendly and sustainable hydrogen fuel. The synergistic effect of the bimetallic components and the nitrogen-doped carbon matrix endow the composite with an optimized electronic structure. The two-electrode alkaline electrolyzer constructed by this heterostructure shows a low cell voltage of 1. This study offers a feasible and facile approach to develop efficient electrocatalysts for water electrolysis, which applies to other electrochemical energy conversion and storage applications.
Tailor-made intrinsically oppositely charged TMC QDs are alternately deposited on the highly ordered MO via a generic ligand-triggered electrostatic interaction to craft heterostructured photoanodes. The charge-transfer pathway stimulated by the photosensitization of TMC QDs is finely tuned by the assembly sequence.
A well-defined and very active single-component manganese II catalyst system for the hydrosilylation of aldehydes and ketones is presented. While the crystal structure of complex 1 has been identified as a binuclear entity, in which the Mn II centers present pentacoordinate coordination spheres, that of complex 2 corresponds to a monomer with a distorted tetrahedral coordination geometry. Complex 2 proved to be a very active precatalyst for the atom-economic hydrosilylation of several aldehydes and ketones under very mild conditions, with a maximum turnover frequency of 95 min—1, via a silyl-Mn II mechanistic route, as asserted by a combination of experimental and theoretical efforts, the respective silanes were cleanly converted to the respective alcoholic products in high yields.
The simulation of X-ray absorption spectra requires both scalar and spin—orbit SO relativistic effects to be taken into account, particularly near L- and M-edges where the SO splitting of core p and d orbitals dominates.
Four-component Dirac—Coulomb Hamiltonian-based linear damped response time-dependent density functional theory 4c-DR-TDDFT calculates spectra directly for a selected frequency region while including the relativistic effects variationally, making the method well suited for X-ray applications.
In this work, we show that accurate X-ray absorption spectra near L2,3- and M4,5-edges of closed-shell transition metal and actinide compounds with different central atoms, ligands, and oxidation states can be obtained by means of 4c-DR-TDDFT.
While the main absorption lines do not change noticeably with the basis set and geometry, the exchange—correlation functional has a strong influence with hybrid functionals performing the best. Finally, the methodology calibrated in this work is used to reproduce the experimental L2,3-edge X-ray absorption spectra of [RuCl2 DMSO 2 Im 2] and [WCl4 PMePh2 2], and resolve the broad bands into separated lines, allowing an interpretation based on ligand field theory and double point groups.
These results support 4c-DR-TDDFT as a reliable method for calculating and analyzing X-ray absorption spectra of chemically interesting systems, advance the accuracy of state-of-the art relativistic DFT approaches, and provide a reference for benchmarking more approximate techniques.
X-ray spectroscopy using high-energy-resolution fluorescence detection HERFD has critically increased the information content in X-ray spectra. We extend this technique to the tender X-ray range and present a study at the L3-edge of molybdenum. We demonstrate that the chemical shift of the L3-edge HERFD spectra follows a parabolic dependence on the oxidation state and show that a qualitative analysis of high-resolution spectra can help to estimate parameters such as distortion of a ligand environment and radial order of atoms around the absorber.
In certain cases, the spectra allow disentangling the contributions from bond lengths and angles to the distortion of the ligand polyhedron. Comparison of the high-resolution spectra with theoretical simulations shows that the single-electron approximation is able to reproduce the spectral shape.
The results of this work may be useful in every branch of physics, inorganic and organometallic chemistry, catalysis, materials science, biochemistry, and mineralogy where observed changes in performance or chemical properties of Mo-based compounds, accompanied by small changes in spectral shape, are to be related to the details of electronic structure and local atomic environment.
A new quaternary telluride, Ba4Ge2Sb2Te10, was synthesized at high temperature via the reaction of elements. Each of the Ge 1 atoms is covalently bonded to four Te atoms, whereas the Ge 2 atom is covalently bonded with one Sb 2 and three Te atoms in a distorted tetrahedral geometry. The title compound is the first example of a chalcogenide that shows Ge—Sb bonding.
The Sb 1 atom is present at the center of the seesaw geometry of four Te atoms. In contrast, the Sb 2 atom forms a seesaw geometry by coordinating with one Ge 2 and three Te atoms. The positive sign of Seebeck coefficient values indicates that the predominant charge carriers are holes in Ba4Ge2Sb2Te Combining metallic and ceramic properties, and as precursors for MXenes, MAX phases have attracted extensive attention.
In recent years, A-element substitution has been demonstrated as an effective scheme to enrich the MAX family. Moreover, the interfacial strength implicating the possibility of exfoliating MAX into MXenes is examined. The A-element plays a crucial role in the lattice parameters and mechanical strength of Ti3AC2, and their variations are well explained by the synergistic effects of d—d and p—d hybridizations between the valence orbitals of Ti and A.
Ti3SbC2 is a mechanical quasi-isotropic configuration. This implies that these configurations are promising precursors for the synthesis of Ti3C2Tx Tx denotes surface groups with a large flake size. Based on the phonon dispersion and electronic structure, these Ti3AC2 configurations might have potential applications in phononic crystals and topological materials. In the race to develop new luminescent materials for the next generation of light-emitting-diode LED -based solid-state lighting and display applications, it is often forgotten that color theory and human perception should be some of the principal factors guiding materials design.
In this Viewpoint, we explore some of the antiquated colorimetrics established originally for incandescent and fluorescent lighting and discuss how they are still widely applied in the literature today to interpret the color quality of luminescent materials, like inorganic phosphors and quantum dots, and to analyze prototype devices, despite their shortcomings. We then shift our analysis toward contemporary ideas in color theory that more accurately describe the color quality of modern LED light bulbs and flat-panel displays.
Finally, the perspective examines the opportunities and challenges of applying these new concepts to guide the design of luminescent materials used in LED-based applications. Herein, we demonstrate that linker installation LI through postsynthesis is an effective strategy to insert emissive second linkers into single-linker-based metal—organic frameworks MOFs to tune the emission properties of multicomponent MOFs.
Full-color emission, including white-light emission, can be achieved via such a LI process. Picosecond time-resolved infrared spectra measured after visible light, nm, and nm excitation revealed excitation-wavelength-dependent deactivation cascades.
The single-beam femtosecond Z-scan measurements were performed to elucidate the third-order nonlinear optical properties, and the temporal response of these porphyrin molecules was investigated using optical pump—probe spectroscopy to study the excited state absorption dynamics. Z-scan measurements revealed that Co-TCBD exhibited a higher nonlinear optical response as compared to free base porphyrins. Furthermore, the femtosecond transient absorption spectroscopy revealed a faster relaxation dynamics of various absorption processes in a picosecond timescale.
The excellent optical limiting threshold 1. Uranyl binitrate complexes have a particular interest in the nuclear industry, especially in the reprocessing of spent nuclear fuel. In this study, the L ligands are two molecules of N,N-di- ethylhexyl isobutyramide DEHiBA monoamide used to bind uranyl in its first coordination sphere. DEHiBA ligands can coordinate uranyl in either trans- or cis-position with respect to the nitrate ligands, and these two conformers may coexist in solution.
To use luminescence spectroscopy as a speciation technique, it is important to determine whether or not these conformers can be discriminated by their spectroscopic properties. The conformation of the pentose ring in nucleotides is extremely important and a basic problem in biochemistry and pharmaceutical chemistry.
Seven types of coordination complexes were developed and characterized using Fourier transform infrared spectroscopy, elemental analysis, thermogravimetric analysis, powder X-ray diffraction, ultraviolet—visible spectroscopy, 1H nuclear magnetic resonance spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction. On the basis of two conformational parameters obtained from single-crystal structure analysis, i.
However, the longest auxiliary ligands [1,4-bis 4-pyridyl -2,3-diaza-1,3-butadiene] cannot limit the flexibility of a nucleotide. Our results demonstrated that the proposed strategy is universal and controllable. Moreover, the chirality of these coordination polymers was examined by combining the explanation of their crystal structures with solid-state circular dichroism spectroscopy measurements.
This approach expands the possibilities for probing the electronic structure in uranyl complexes beyond the strongly covalent U—O bonds. Transition-metal phosphates show a wide range of chemical compositions, variations of the valence states, and crystal structures. They are commercially used as solid-state catalysts, cathode materials in rechargeable batteries, or potential candidates for proton-exchange membranes in fuel cells.
In Ti III p, trivalent titanium ions occupy the center of TiO6 polyhedra, coordinated by five pyrophosphate groups, one of them as a bidentate ligand. This secondary coordination causes the formation of one-dimensional six-membered ring channels with a diameter dmax of 3.
The specific proton conductivity and activation energy of the proton migration of Ti III p, governed by the Grotthus mechanism, belong to the highest and lowest, respectively, ever reported for this class of materials, which reveals its potential application in electrochemical devices like fuel cells and water electrolyzers in the intermediate temperature range. Multiresponsive materials can adapt to numerous changes in their local environment, which makes them highly valuable for various applications.
Although nanostructured and polymeric multiresponsive materials are plentiful, small-molecule analogues are scarce. Complex 18C6-PtII responds to i cationic guests, producing changes in luminescence in both solution and the solid state, ii solvent molecules, which perturb the packing of the complex in the solid state and cause reversible color changes, and iii solvent polarity, which leads to controlled aggregation.
These responses may enable 18C6-PtII to function as a sensor for ions and solvents, or as a functional unit for the fabrication of hybrid supramolecular polymers and metallogels. The development of sustainable catalysts to get methanol from CO2 under milder conditions and without any additives is still considered an arduous task. In many instances, transition-metal-catalyzed carbon dioxide to formic acid formation is more facile than methanol formation.
This article provides comprehensive density functional theoretic investigations of six new Mn I PNN complexes, which are designed to perform CO2 to methanol conversion under milder reaction conditions. All these computationally modeled Mn I PNN complexes demonstrate the promising catalytic activity to get methanol through cascade catalytic cycles at The metal—ligand cooperative MLC as well as noncooperative NC pathways are investigated for each catalytic cycle.
The NC pathway is the preferred pathway for formic acid and formaldehyde formation, whereas methanol formation proceeds through only the MLC pathway. SPCAT04 is found to be a better catalyst for the selective formation of formic acid formation at room temperature than the rest of the catalysts. The computed TOF results are found reliable upon comparison with experimentally established catalysts.
To establish the structure—activity relationship, the activation strain model and Fukui function calculations are performed on all the catalysts. Both these studies provide complementary results. The present study revealed a very important finding that a more electrophilic metal center could facilitate the CO2 hydrogenation reaction robustly. All computationally designed catalysts could be cheaper and better alternatives to convert CO2 to methanol under mild reaction conditions in an aqueous medium.
Ligand substitution at the metal center is common in catalysis and signal transduction of metalloproteins. Understanding the effects of particular ligands, as well as the polypeptide surrounding, is critical for uncovering mechanisms of these biological processes and exploiting them in the design of bioinspired catalysts and molecular devices.
The differences in the hydrogen-bonding interactions in folded proteins and in solvation of unbound X in the unfolded proteins explain these trends. Experimental rate constants for X dissociation in differently ligated cyt c variants are consistent with this sequence, but the differences between Met and His dissociation rates are attenuated because the former process is limited by the heme crevice opening.
Analyses of activation parameters and comparisons to those for the Lys-to-Met ligand switch in the alkaline transition suggest that ligand dissociation is entropically driven in all the variants and accompanied by Lys protonation at neutral pH.
The described thiolate redox-linked switches have offered a wealth of new information about interactions of different protein-derived ligands with the heme iron in cyt c model proteins, and we anticipate that the strategy of employing these switches could benefit studies of other redox metalloproteins and model complexes. Pair your accounts. Your Mendeley pairing has expired. Please reconnect. Get e-Alerts.
Latest Article January 13, January 13, Kuznetsov , and S. Johnson , Jeffrey J. Liu , Adam D. Samuel , Ralf Haiges , and Smaranda C. Siebert , Keene Patarakun , and Christina S. ACS AuthorChoice.
Abstract Full text PDF ABSTRACT In order to expand and exploit the useful properties of d6-iron II and d5-iron III complexes in potential magnetic, photophysical, or magnetooptical applications, crucial ligand-controlled parameters are the ligand field strength in a given coordination mode and the availability of suitable metal and ligand frontier orbitals for charge-transfer processes.
Eckhardt , Martin-Louis Y. Pietro and A. Aleksandrov , Georgi N. Tawse , Clemens Ritter , and Abbie C. Mahmoud , Zeinhom M. Smith , Mehran Amiri , Nicolas P. Martin , Alice Lulich , Lauren N. Palys , Guomin Zhu , James J. Blackaby , Katie L. Harriman , Samuel M. Mahon , Damien M. Tailoring Thermal Expansion of LiFe 0. Borah , Farnaz Yashmin , and Ankur K. Sivchenko , Felix Bacher , Kelvin K. Lyubov , Galina A. Gurina , Yulia V. Escalona , Frank W.
McConnell , Nicholas C. Skubi , Reagan X. Hooper , Brandon Q. Mercado , Melissa M. Bollmeyer , Samantha N. MacMillan , Kyle M. Lancaster , and Patrick L. What Singles out Aluminyl Anions? Mihaly , Steven M. Wolf , Alexis T. Grusenmeyer , Stephanie Collins , and Thomas G. Abstract Full text PDF ABSTRACT Controlling the structure of halide perovskites through component engineering, and thus revealing the changes in luminescence properties caused by the conversion of crystal structure, is of great significance.
Rodriguez , Dietrich R. Kunchur and Maravanji S. Carroll , Karsten Meyer , and Daniel J.
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