A Phenanthrenequinone-Based Ratiometric Fluorescent Probe for Rapid Detection of Peroxynitrite with Imaging in Osteoblast Precursor Cells.

In the current situation, peroxynitrite (ONOO-) is drawing the increasing attention of researchers for its pivotal role in diverse pathological and physiological processes on grounds of robust oxidation and nitrification. Herein, we have successfully designed and synthesized a phenanthrenequinone benzyl borate-based chemosensor for fast and selective detection of ONOO-. The probe PTDP itself had an orange fluorescence, which was changed to strong blue fluorescence upon the addition of ONOO-, indicating the ratiometric response of the probe. This is so because of the cleavage of the benzyl boronate-protecting group of PTDP upon the addition of ONOO- with simultaneous releasing of pyridinyl-based chemosensor PPI. The PTDP showed outstanding performance in the various photophysical studies such as good selectivity, excellent sensitivity with a very low detection limit of 2.74 nM, and a very fast response time (<15 s). Furthermore, for practical applicability, it was successfully applied in the ratiometric detection of ONOO- in osteoblast precursor cells.

A density functional theory analysis of the C-H activation reactivity of iron(IV)-oxo complexes with an 'O' substituted tetramethylcyclam macrocycle.

In this article, we present a meticulous computational study to foresee the effect of an oxygen-rich macrocycle on the reactivity for C-H activation. For this study, a widely studied nonheme Fe(IV)O molecule with a TMC (1,4,8,11-tetramethyl 1,4,8,11-tetraazacyclotetradecane) macrocycle that is equatorially attached to four nitrogen atoms (designated as N4) and acetonitrile as an axial ligand has been taken into account. For the goal of hetero-substitution, step-by-step replacement of the N4 framework with O atoms, i.e., N4, N3O1, N2O2, N1O3, and O4 systems, has been considered, and dihydroanthracene (DHA) has been used as the substrate. In order to neutralise the system and prevent the self-interaction error in DFT, triflate counterions have also been included in the calculations. The study of the energetics of these C-H bond activation reactions and the potential energy surfaces mapped therefore reveal that the initial hydrogen abstraction, which is the rate-determining step, follows the two-state reactivity (TSR) pattern, which means that the originally excited quintet state falls lower in the transition state and the product. The reaction follows the hydrogen atom transfer (HAT) mechanism, as indicated by the spin density studies. The results revealed a fascinating reactivity order, in which the reactivity increases with the enrichment of the oxygen atom in the equatorial position, namely the order follows N4 < N3O1 < N2O2 < N1O3 < O4. The impacts of oxygen substitution on quantum mechanical tunneling and the H/D kinetic isotope effect have also been investigated. When analysing the causes of this reactivity pattern, a number of variables have been identified, including the reactant-like transition structure, spin density distribution, distortion energy, and energies of the electron acceptor orbital, i.e., the energy of the LUMO (σ*z2), which validate the obtained outcome. Our results also show very good agreement with earlier combined experimental and theoretical studies considering TMC and TMCO-type complexes. The DFT predictions reported here will undoubtedly encourage experimental research in this biomimetic field, as they provide an alternative with higher reactivity in which heteroatoms can be substituted for the traditional nitrogen atom.

Experimental and computational investigation of the α-amylase catalyzed Friedel-Crafts reaction of isatin to access symmetrical and unsymmetrical 3,3',3''-trisindoles.

Trisindoles are of tremendous interest due to their wide range of biological activities. In this context, a number of methods have been reported in the past to synthesize 3,3',3''-trisindoles. However, most of the methods are only able to produce symmetrical 3,3',3''-trisindoles. Herein, we develop a sustainable and efficient approach to synthesize symmetrical as well as unsymmetrical 3,3',3''-trisindoles in a very selective manner using the α-amylase enzyme as a catalyst. Furthermore, various differently substituted isatin and indoles were used to prove the generality of the protocol and symmetrical or unsymmetrical 3,3',3''-trisindoles were obtained in 43-97% isolated yields. Next, a probable mechanism is proposed and investigated using molecular dynamics (MD) investigation to gain more insight into the role of residues available in the active site of the α-amylase enzyme. These studies revealed that Glu230, Lys209, and Asp206 in the active site of α-amylase play an important role in this catalysis. Moreover, the DFT studies suggested the formation of bisindole and alkylideneindolenine intermediates during the transformation. We synthesized four different biologically important 3,3',3''-trisindoles on a gram scale, which proved the robustness and scalability of this protocol.

High-valent nonheme Fe(IV)O/Ru(IV)O complexes catalyze C-H activation reactivity and hydrogen tunneling: a comparative DFT investigation.

A comprehensive density functional theory investigation has been presented towards the comparison of the C-H activation reactivity between high-valent iron-oxo and ruthenium-oxo complexes. A total of four compounds, e.g., [Ru(IV)O(tpy-dcbpy)] (1), [Fe(IV)O(tpy-dcbpy)] (1'), [Ru(IV)O(TMCS)] (2), and [Fe(IV)O(TMCS)] (2'), have been considered for this investigation. The macrocyclic ligand framework tpy(dcbpy) implies tpy = 2,2':6',2''-terpyridine, dcbpy = 5,5'-dicarboxy-2,2'-bipyridine, and TMCS is TMC with an axially tethered -SCH2CH2 group. Compounds 1 and 2' are experimentally synthesized standard complexes with Ru and Fe, whereas compounds 1' and 2 were considered to keep the macrocycle intact when switching the central metal atom. Three reactants including benzyl alcohol, ethyl benzene, and dihydroanthracene were selected as substrates for C-H activation. It is noteworthy to mention that Fe(IV)O complexes exhibit higher reactivity than those of their Ru(IV)O counterparts. Furthermore, regardless of the central metal, the complex featuring a tpy-dcbpy macrocycle demonstrates higher reactivity than that of TMCS. Here, a thorough analysis of the reactivity-controlling characteristics-such as spin state, steric factor, distortion energy, energy of the electron acceptor orbital, and quantum mechanical tunneling-was conducted. Fe(IV)O exhibits the exchanged enhanced two-state-reactivity with the quintet reactive state, whereas Ru(IV)O has only a triplet reactive state. Both the distortion energy and acceptor orbital energy are low in the case of Fe(IV)O supporting its higher reactivity. All the investigated C-H activation processes involve a significant contribution from hydrogen tunneling, which is more pronounced in the case of Ru, although it cannot alter the reactivity pattern. Furthermore, it has also been found that, independent of the central metal, aliphatic hydroxylation is always preferable to aromatic hydroxylation. Overall, this work is successful in establishing and investigating the cause of enzymes' natural preference for Fe over Ru as a cofactor for C-H activation enzymes.

Computational identification and exploration of novel FGFR tyrosine kinase inhibitors for the treatment of cholangiocarcinoma.

Tyrosine kinase inhibitors are a specific drug class revolutionizing cancer treatment. FGFR (Fibroblast Growth Factor Receptor) is a member of the receptor tyrosine kinase family that has been involved in various alterations which have been increasingly recognized as critical molecular drivers in cholangiocarcinoma, a malignant tumor originating from bile duct epithelial cells. The paper focuses on stepwise computational investigations for the discovery of novel inhibitors of FGFR using pharmacophore modeling, virtual screening, docking, ADMET analysis, molecular dynamics, and knowledge-based structure-activity relationship. To begin with, we have considered a library of 120314868 compounds from the ZINC 15 database through pharmacophore modeling, which was narrowed down to 110 having binding affinity >-8.0 kcal mol-1. The 110 compounds were analyzed using virtual screening and compared with the FDA-approved drug pemigatinib, which provided the 34 hits with binding affinities >-6.5 kcal mol-1. Finally, the top 4 hits were considered for docking, and ADMET property analysis for drug-likeness. MD and MM-GBSA analysis were performed to predict the binding free energy of these chemicals and determine their stability. To gain insight into the structure and binding interactions of these compounds, knowledge-based SAR analyses were performed using their electrostatic potential maps computed with DFT. Several techniques were employed to build improved inhibitors based on these SAR, and they were then analyzed utilizing ADMET, MD studies, and MM-GBSA analyses. Finally, the results suggested that the identified four compounds and developed inhibitors from this current work can be employed effectively as prospective FGFR inhibitors for treating Cholangiocarcinoma.Communicated by Ramaswamy H. Sarma.

N-Heterocyclic imino-catalyzed 1,4-regioselective azide-alkyne cycloaddition (AAC): a metal-free approach.

An unprecedented synthetic approach has been devised to efficiently synthesize regioselective 1,4-disubstituted 1,2,3-triazoles. This technique relies on the use of innovative metal-free highly basic N-heterocyclic imino catalysts. The experimental observations have been supported further by TD-DFT computational studies.

Divergent and Selective Synthesis of 3-Alkylidene Oxindoles Using Pd-Catalyzed Multicomponent Reaction.

Herein, a divergent and selective synthesis of (E)-3-alkylidene oxindole, which is a highly valuable framework due to its presence in biologically important molecules, via palladium-catalyzed multicomponent reaction of 3-diazo oxindole, isocyanide, and aniline has been developed. Further, the feasibility of the reaction was demonstrated by employing differently substituted 3-diazo oxindoles, isocyanides, and anilines as starting material and obtaining the corresponding products in 31-83% isolated yields. Besides, a plausible mechanism has been presented and further investigated using DFT calculations which suggest the formation of the Pd-carbene complex and ketenimine intermediate as the key step during the catalytic cycle.

A 'double locked' ratiometric fluorescent probe for detection of cysteine in a viscous system and its application in cancer cells.

Intracellular viscosity is a physicochemical property that regulates the consequences of several biological progressions. Cysteine (Cys) is an important signaling molecule that commands many cellular activities, such as antioxidant generation. Predicting that both may be interconnected with a diversity of pathological processes, their contemporaneous measurement would be valuable for studying the pathological ailment of cells. Herein, we have synthesized a 'double locked' probe, acrylic acid 6-[4-(2-benzothiazol-2-yl-2-cyano-vinyl)-phenyl]-naphthalen-2-yl ester (ABN) for the detection of Cys in a viscous medium and explored its application to living cells that were exposed to dexamethasone to regulate the intracellular viscosity level. ABN displayed a satisfactory ratiometric (blue to orange) fluorescence response in solution and in living cells when Cys and viscosity coexisted. A turn-on fluorescence signal was visualized when the probe was individually treated with Cys and glycerol (a standard viscosity source). Therefore, we propose that ABN is a fluorescent probe that permits the monitoring of variations in intracellular viscosity and Cys levels in a biological environment, and it can be utilized in innumerable cellular damage models.

Recent advances in transition metal-mediated trifluoromethylation reactions.

Fluorine compounds are known for their abundance in more than 20% of pharmaceutical and agrochemical products mainly due to the enhanced lipophilicity, metabolic stability and pharmacokinetic properties of organofluorides. Consequently, the last decade has seen enormous growth in the incorporation of a trifluoromethyl group into organic motifs. With due significance, this review aims to provide a complete picture of the transition metal-mediated construction of C(sp3, sp2, and sp)-CF3 bonds via C-H/X bond functionalization or addition processes in both aliphatic and aromatic hydrocarbons. Diversified reagents ranging from radical and electrophilic to nucleophilic trifluoromethylating agents and their respective mechanisms have been further deliberated in this comprehensive overview. The comprehensive coverage on this topic is expected to make this review unique and beneficial for further future applications enriching the community towards further improvements in the field of trifluoromethylation reactions, in turn improving the propensity towards further development of agrochemical drugs.

Role of "S" Substitution on C-H Activation Reactivity of Iron(IV)-Oxo Cyclam Complexes: a Computational Investigation.

A comprehensive density functional theory (DFT) investigation has been presented in this article to address the role of equatorial sulfur ligation in C-H activation. A non-heme iron-oxo compound with four nitrogen atoms constituting the equatorially connected macrocyclic framework (represented as N4) [Fe(IV)═O(THC)(CH3CN)]2+(THC = 1,4,8,11-tetrahydro1,4,8,11-tetraazacyclotetradecane) has been considered as the base compound. Other complexes have been anticipated by the sequential replacement of this nitrogen by sulfur, that is, N4, N3S1, N2S2, N1S3, and S4. Counterions, as always, have been considered to avoid the self-interaction error in DFT. Generally, the anti-conformers (with respect to equatorial N-H and Fe═O) turned out to be the most stable. It was found that with the enrichment of the equatorial sulfur atom, reactivity increases successively, that is, we get the trend N4 < N3S1 < N2S2 < N1S3 < S4. Our investigations have also verified the available experimental results where it has been reported that N2S2 is more reactive than N4 in their mixed conformation. In search of insights into this typical pattern of reactivity, the interplay of several factors has been recognized, such as the distortion energy which decreases for the transition states with the addition of sulfur; the spin density on the oxygen atom which increases implying that the radical character of abstractor increases on sulfur ligation; the energy of the electron acceptor orbital (the lowest unoccupied molecular orbital (σz2*)) which decreases continuously with the sulfur substitution; and the triplet-quintet oxidant energy gap which decreases consistently with S enrichment in the equatorial position. The computational predictions reported here, if further validated by experiments, will definitely encourage the synthesis of sulfur-ligated bio-inspired complexes instead of the ones constituting nitrogen exclusively.

A Dual Functional 2D MOF Exhibiting Rare Photosalient Effect as well as Selective Pd(II) Sensing in Aqueous Medium.

A Zn(II) based two-dimensional metal-organic framework (2D MOF) [Zn2(suc)2(4-nvp)2] (1) [H2suc = succinic acid and 4-nvp = 4-(1-naphthylvinyl)pyridine] exhibits a "photosalient effect" under UV light as well as sunlight along with the release of a stereoselective cyclobutane ligand, 1,3-bis(4'-pyridyl)-2,4-bis(naphthyl)cyclobutane (rctt-4-pncb). Photolysis of in situ generated MOF in solution also leads to the formation of rctt-4-pncb crystals. Interestingly, compound 1 shows a high selectivity for Pd(II) sensing in aqueous medium.

Transition-metal-catalyzed C-H bond alkylation using olefins: recent advances and mechanistic aspects.

Transition metal catalysis has contributed immensely to C-C bond formation reactions over the last few decades, and alkylation is no exception. The superiority of such methodologies over traditional alkylation is evident from minimal reaction steps, shorter reaction times, and atom economy while also allowing control over regio- and stereo-selectivity. In particular, hydrocarbonation of alkenes has grabbed increased attention due its fundamental ability to effectively and selectively synthesise a wide range of industrially and pharmaceutically relevant moieties. This review attempts to provide a scientific viewpoint and a systematic analysis of the recent developments in transition-metal-catalyzed alkylation of various C-H bonds using simple and activated olefins. The key features and mechanistic studies involved in these transformations are described briefly.

Effect of the substituent on C-H activation catalyzed by a non-heme Fe(IV)O complex: a computational investigation of reactivity and hydrogen tunneling.

Density functional theory investigations were performed to address the C-H activation reactivity and the influence of quantum mechanical tunneling catalyzed by a non-heme iron(IV)-oxo complex, namely [FeIVOdpaq-X]+, where the macrocyclic ligand dpaq represents {2-[bis(pyridine-2-yl-methyl)]amino-N-quinolin-8-yl-acetamido}. Counter ion and solvent corrections were incorporated in the computation to avoid self-interaction error. To find the impact of the indirectly linked substituents to the central metal atom, Fe, the macrocyclic ligand dpaq was substituted at the 5-position of its quinoline moiety represented as dpaq-X and the reactivity and hydrogen tunneling were compared with the parent ligand dpaq-H. Here, both electron-donating, e.g. -N(CH3)2 and -OMe, and electron-withdrawing, e.g. -NO2 and -SO2CF3, substituents compared to hydrogen were considered. The reactions displayed exchange interaction favouring two-state reactivity (TSR) as the S = 2 state was found for the excited state in the reactant, which crossed the S = 1 path (initially the ground state) during the progress of the reaction. This was further verified by the tunneling corrected kinetic isotope effect (KIE), which closely matched with the experiment (32) in the S = 2 state (22), whereas the S = 1 KIE (∼69) was found to be very far from that experimentally observed. More than 90% of all the C-H activation reactions proceeded through quantum mechanical tunneling even at room temperature. As the substituent group became more electron-donating, both the tunneling contributions and the kinetic isotope effect increased, which supported the anti-electrophilic tunneling control reactivity premise. The presented consequences may further expose the possibility for the rational design of metal-based catalysts with systematic ligand/substituent tuning that can be performed efficiently through quantum mechanical tunneling.

A Pd-catalyzed one-pot cascade consisting of C-C/C-O/N-N bond formation to access benzoxazine fused 1,2,3-triazoles.

A Pd-catalyzed one-pot cascade consisting of C-C/C-O/N-N bond formation to access clinically important fused 1,2,3-triazoles using N-aryl-α-(tosylhydrazone)acetamides with isocyanide has been developed. Besides, various substitutions on the N-aryl part of acetamides along with different isocyanides show good compatibility in this protocol. Next, two plausible mechanistic routes were proposed; however, one of the routes was more favourable which involved the formation of a benzoxazine ring first followed by the realization of a triazole ring. Additionally, the more favourable mechanistic route was investigated using DFT studies which suggests that the formations of a Pd(II)-isocyanide complex and α-diazoimino intermediates were key steps in the catalytic cycle.

Fabrication of self-assembled nanostructures for intracellular drug delivery from diphenylalanine analogues with rigid or flexible chemical linkers.

Self-assembly of molecular building blocks is a simple and useful approach to generate supramolecular structures with varied morphologies and functions. By studying the chemical properties of the building blocks and tuning the parameters of their self-assembly process, the resultant supramolecular assemblies can be optimized for the required downstream applications. To this end, in the present study we have designed and synthesized three different molecular building blocks composed of two diphenylalanine (FF) units connected to each other through three different linkers: ethylenediamine, succinic acid, or terephthalaldehyde. Under identical conditions, all the three building blocks self-assemble into supramolecular architectures with distinct morphologies. However, by varying the polarity of the self-assembly medium, the nature of the non-covalent interactions changes in such a way as to generate additional self-assembled structures unique to each building block. Utilizing microscopic and spectroscopic techniques, we characterized the morphological variety generated by each building block/linker combination. These data represent the first report analysing the diversity of nanostructures that can be generated from identical dipeptide-based molecular backbones simply by varying the chemical linker. We also demonstrate that the spherical assemblies and nanorod structures fabricated from these dipeptide/linker pairs can act as drug delivery systems. More specifically, the spherical assembly generated by two FF dipeptides linked via ethylenediamine and nanorods fabricated from terephthalaldehyde linked FF dipeptides were able to encapsulate the cancer chemotherapeutic agent doxorubicin (DOX) and chaperone the drug into cells. Thus, these supramolecular assemblies represent a new platform for the development of efficient and effective intracellular drug delivery systems.

Quantum-Dot-Mediated Controlled Synthesis of Dual Oxides of Molybdenum from MoS2 : Quantification of Supercapacitor Efficacy.

The versatile technological applications of molybdenum oxides requires the efficient synthesis of various stoichiometric molybdenum oxides. Thus, herein, a controlled method to synthesize both MoO3 and MoO2 from MoS2 via quantum dot intermediates is reported. Microscopic, spectroscopic, and X-ray studies corroborate the formation of orthorhombic α-MoO3 with a microbelt structure and monoclinic MoO2 nanoparticles that self-assemble into hollow tubes. Quantitative investigations into charge-storage kinetics reveal that MoO2 exhibits an excellent pseudocapacitive response up to a mass loading of 5 mg cm-2 with an areal capacity of 327.2 mC cm-2 at 5 mV s-1 , with 41.9 % retention at 100 mV s-1 . In contrast, above a mass loading of 0.5 mg cm-2 , the charge-storage nature of MoO3 electrodes switches from that of a supercapacitor to battery type. At a sweep rate of 50 mV s-1 , 87.2 % of the total charge is contributed by a capacitive response in a 1 mg cm-2 MoO2 electrode. The charge-storage kinetics of MoO3 and MoO2 reflect on the respective asymmetric supercapacitors. A MoO2 //graphite asymmetric supercapacitor holds an outstanding energy density of 341 mW h m-2 at a power density of 4949 mW m-2 and delivers an ultrahigh power density of 28140 mW m-2 with an energy density 142 mW h m-2 and energy efficiency of 87 %.

Structure and reactivity/selectivity control by oriented-external electric fields.

This is a tutorial on use of external-electric-fields (EEFs) as effectors of chemical change. The tutorial instructs readers how to conceptualize and design electric-field effects on bonds, structures, and reactions. Most effects can be comprehended as the field-induced stabilization of ionic structures. Thus, orienting the field along the "bond axis" will facilitate bond breaking. Similarly, orienting the field along the "reaction axis", the direction in which "electron pairs transform" from reactants- to products-like, will catalyse the reaction. Flipping the field's orientation along the reaction-axis will cause inhibition. Orienting the field off-reaction-axis will control stereo-selectivity and remove forbidden-orbital mixing. Two-directional fields may control both reactivity and selectivity. Increasing the field strength for concerted reactions (e.g., Diels-Alder's) will cause mechanistic-switchover to stepwise mechanisms with ionic intermediates. Examples of bond breaking and control of reactivity/selectivity and mechanisms are presented and analysed from the "ionic perspective". The tutorial projects the unity of EEF effects, "giving insight and numbers".

Catalysis of Methyl Transfer Reactions by Oriented External Electric Fields: Are Gold-Thiolate Linkers Innocent?

Oriented external electric fields (OEEFs) are potent effectors of chemical change and control. We show that the Menshutkin reaction, between substituted pyridines and methyl iodide, can be catalyzed/inhibited at will, by just flipping the orientation of the EEF ( F Z) along the "reaction axis" ( Z), N---C---I. A theoretical analysis shows that catalysis/inhibition obey the Bell-Evans-Polanyi principle. Significant catalysis is predicted also for EEFs oriented off the reaction axis. Hence, the observation of catalysis can be scaled up and may not require orienting the reactants vis-à-vis the field. It is further predicted that EEFs can also catalyze the front-side nucleophilic displacement reaction, thus violating the Walden-inversion paradigm. Finally, we considered the impact of gold-thiolate linkers, used experimentally to deliver the EEF stimuli, on the Menshutkin reaction. A few linkers were tested and proved not to be innocent. In the presence of F Z, the linkers participate in the electronic reorganization of the molecular system. In so doing, these linkers induce local electric fields, which map the effects of the EEF and induce catalysis/inhibition at will, as in the pristine reaction. However, as the EEF becomes more negative than -0.1 V/Å, an excited charge transfer state (CTS), which involves one-electron transfer from the 5p lone pair of iodine to an antibonding orbital of the gold cluster, crosses below the closed-shell state of the Menshutkin reaction and causes a mechanistic crossover. This CTS catalyzes nucleophilic displacement of iodine radical from the CH3I•+ radical cation. The above predictions and others discussed in the text are testable.

Kinetic Isotope Effect Determination Probes the Spin of the Transition State, Its Stereochemistry, and Its Ligand Sphere in Hydrogen Abstraction Reactions of Oxoiron(IV) Complexes.

This Account outlines interplay of theory and experiment in the quest to identify the reactive-spin-state in chemical reactions that possess a few spin-dependent routes. Metalloenzymes and synthetic models have forged in recent decades an area of increasing appeal, in which oxometal species bring about functionalization of hydrocarbons under mild conditions and via intriguing mechanisms that provide a glimpse of Nature's designs to harness these reactions. Prominent among these are oxoiron(IV) complexes, which are potent H-abstractors. One of the key properties of oxoirons is the presence of close-lying spin-states, which can mediate H-abstractions. As such, these complexes form a fascinating chapter of spin-state chemistry, in which chemical reactivity involves spin-state interchange, so-called two-state reactivity (TSR) and multistate reactivity (MSR). TSR and MSR pose mechanistic challenges. How can one determine the structure of the reactive transition state (TS) and its spin state for these mechanisms? Calculations can do it for us, but the challenge is to find experimental probes. There are, however, no clear kinetic signatures for the reactive-spin-state in such reactions. This is the paucity that our group has been trying to fill for sometime. Hence, it is timely to demonstrate how theory joins experiment in realizing this quest. This Account uses a set of the H-abstraction reactions of 24 synthetic oxoiron(IV) complexes and 11 hydrocarbons, together undergoing H-abstraction reactions with TSR/MSR options, which provide experimentally determined kinetic isotope effect (KIEexp) data. For this set, we demonstrate that comparing KIEexp results with calculated tunneling-augmented KIE (KIETC) data leads to a clear identification of the reactive spin-state during H-abstraction reactions. In addition, generating KIEexp data for a reaction of interest, and comparing these to KIETC values, provides the mechanistic chemist with a powerful capability to identify the reactive-TS in terms of not only its spin state but also its geometry and ligand-sphere constitution. Since tunneling "cuts through" barriers, it serves as a chemical selectivity factor. Thus, we show that in a family of oxoirons reacting with one hydrocarbon, the tunneling efficiency increases as the ligands become better electron donors. This generates counterintuitive-reactivity patterns, like antielectrophilic reactivity, and induces spin-state reactivity reversals because of differing steric demands of the corresponding 2S+1TS species, etc. Finally, for the same series, the Account reaches intuitive understanding of tunneling trends. It is shown that the increase of ligand's donicity results in electrostatic narrowing of the barrier, while the decrease of donicity and increase of bond-order asymmetry in the TS (inter alia due to Bell-Evans-Polanyi effects) broadens the barrier. Predictions are made that usage of powerful electron-donating ligands may train H-abstractors to activate the strongest C-H bond in a molecule. The concepts developed here are likely to be applicable to other oxometals in the d- and f-blocks.

A New Facile Synthesis of Tungsten Oxide from Tungsten Disulfide: Structure Dependent Supercapacitor and Negative Differential Resistance Properties.

Tungsten oxide (WO3 ) is an emerging 2D nanomaterial possessing unique physicochemical properties extending a wide spectrum of novel applications which are limited due to lack of efficient synthesis of high-quality WO3 . Here, a facile new synthetic method of forming WO3 from tungsten sulfide, WS2 is reported. Spectroscopic, microscopic, and X-ray studies indicate formation of flower like aggregated nanosized WO3 plates of highly crystalline cubic phase via intermediate orthorhombic tungstite, WO3. H2 O phase. The charge storage ability of WO3 is extremely high (508 F g-1 at current density of 1 A g-1 ) at negative potential range compared to tungstite (194 F g-1 at 1 A g-1 ). Moreover, high (97%) capacity retention after 1000 cycles and capacitive charge storage nature of WO3 electrode suggest its supremacy as a negative electrode of supercapacitors. The asymmetric supercapacitor, based on the WO3 as a negative electrode and mildly reduced graphene oxide as a positive electrode, manifests high energy density of 218.3 mWhm-2 at power density 1750 mWm-2 , and exceptionally high power density, 17 500 mW m-2 , with energy density of 121.5 mWh m-2 . Furthermore, the negative differential resistance (NDR) property of both WO3 and WO3 .H2 O are reported for the first time and NDR is explained with density of state approach.