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A previous report demonstrated that EuDO3A could be used as an NMR shift reagent for imaging extracellular lactate produced by cancer cells using CEST imaging. In this work, a series of heptadentate macrocyclic YbDO3A-trisamide complexes with δ-chiral carbons in the three pendant side-arms were examined as shift reagents for lactate detection. High resolution ¹H NMR spectra and DFT calculations provided evidence for the formation of stereoselective lactate·YbDO3Atrisamide complexes each with a different CEST signature. This stereoselectivity allowed discrimination of D- versus L-lactate by both high-resolution NMR and CEST. This work demonstrates that lanthanide-based paramagnetic shift reagents can be designed to detect important metabolites by CEST MRI selectively. [ABSTRACT FROM AUTHOR]

The use of biomimetic approaches toward the production of nonsolid yet functional architectures holds potential for the emergence of novel device concepts. Gels, in particular those obtained via self-assembly of π-conjugated molecules, are dynamic materials possessing unique (opto)-electronic properties. Their adaptive nature imparts unprecedented responsivity to various stimuli. Hitherto, a viable device platform to electrically probe in situ a sol--gel transition is still lacking. Here we describe the fabrication of a sub-micrometer electrodic cavity, which enables low-voltage electrical operation of π-gels. Thanks to the in situ supramolecular self-assembly of the π-gelator occurring within the cavity, we conceived a novel gelbased memristor whose sol--gel transition is reversible and can be controlled via heating and dc bias. This work opens perspectives toward the fabrication of a novel generation of nonsolid multiresponsive devices. [ABSTRACT FROM AUTHOR]

A general and efficient method for accessing enantiomerically pure arylpyrroles by utilizing the catalytic asymmetric Paal-Knorr reaction has been developed for the first time. A wide range of axially chiral arylpyrroles were obtained in high yields with good to excellent enantioselectivities. The key to success is the use of the combined-acid catalytic system involving a Lewis acid and a chiral phosphoric acid for achieving effective enantiocontrol. Noteworthy is that an unexpected solvent-dependent inversion of the enantioselectivity was observed in the above-mentioned asymmetric reaction. [ABSTRACT FROM AUTHOR]

We report a 3.6 nm Ti52--oxo cluster with precise atomic structure, which presents a largest size record in the family of titanium--oxo clusters (TOCs). The crystal growth of such large Ti52 is based on a stepwise interlayer assembly approach from Ti6 substructures. The possible growth mechanism of Ti52 could be deduced from crystal structures of two substructures, Ti6 and Ti17, which were also synthesized under similar conditions as Ti52. Moreover, these TOCs show cluster-size-dependent photocatalytic hydrogen evolution activities with Ti52 giving a H2 production rate up to 398 μmol/h/g, which is also the highest record in the family of TOCs. This work not only represents a milestone in constructing large TOCs with comparable sizes as TiO2 nanoparticles but also brings significant advances in improving photocatalytic behaviors of TOCs. [ABSTRACT FROM AUTHOR]

Harnessing surface plasmon of metal nanostructures to promote catalytic organic synthesis holds great promise in solar-to-chemical energy conversion. High conversion efficiency relies not only on broadening the absorption spectrum but on coupling the harvested energy into chemical reactions. Such coupling undergoes hot-electron transfer and photothermal conversion during the decay of surface plasmon; however, the two plasmonic effects are unfortunately entangled, making their individual roles still under debate. Here, we report that in a model system of bimetallic Au-Pd core-shell nanostructures the two effects can be disentangled through tailoring the shell thickness at atomic-level precision. As demonstrated by our ultrafast absorption spectroscopy characterizations, the achieved tunability of the two effects in a model reaction of Pd-catalyzed organic hydrogenation offers a knob for enhancing energy coupling. In addition, the two intrinsic plasmonic modes at 400-700 and 700-1000 nm in the bar-shaped nanostructures allow for utilizing photons to a large extent in full solar spectrum. This work establishes a paradigmatic guidance toward designing plasmonic-catalytic nanomaterials for enhanced solar-to-chemical energy conversion. [ABSTRACT FROM AUTHOR]

The synthesis, structure, and reactivity of a uranium metallacyclopropene were comprehensively studied. Reduction of (η5-C5Me5)2UCl2 (1) with potassium graphite (KC8) in the presence of bis(trimethylsilyl)acetylene (Me3SiC≡CSiMe3) allows the first stable uranium metallacyclopropene (η5-C5Me5)2U[η2-C2(SiMe3)2] (2) to be isolated. Magnetic susceptibility data confirm that 2 is a U(IV) complex, and density functional theory (DFT) studies indicate substantial 5f orbital contributions to the bonding of the metallacyclopropene U-(η2-C=C) moiety, leading to more covalent bonds between the (η5-C5Me5)2U2+ and [η2-C2(SiMe3)2]2- fragments than those in the related Th(IV) compound. Consequently, very different reactivity patterns emerge, e.g., 2 can act as a source for the (η5-C5Me5)2U(II) fragment when reacted with alkynes and a variety of heterounsaturated molecules such as imines, bipy, carbodiimide, organic azides, hydrazine, and azo derivatives. [ABSTRACT FROM AUTHOR]

The selective preparation of 1,1,1-tris-(boronates) from vinylarenes and bis(pinacolato)diboron is described. The reactions occur at ambient temperature with excellent selectivity, high yields, and good functional group tolerance. Mechanistic studies suggest that Co(l)-catalyzed double dehydrogenative borylations generate a 1,1-diborylalkene intermediate, which undergoes hydroboration with pinacolborane formed in situ to yield 1,1,1-tris(boronate). [ABSTRACT FROM AUTHOR]

In classical transition state theory, a transition state is connected to its reactant(s) and product(s). Recently, chemists found that reaction pathways may bifurcate after a transition state, leading to two or more sets of products. The product distribution for such a reaction containing a bifurcating potential energy surface (bPES) is usually determined by the shape of the bPES and dynamic factors. However, if the bPES leads to two intermediates (other than two products), which then undergo further transformations to give different final products, what factors control the selectivity is still not fully examined. This missing link in transition state theory is founded in the present study. Aiming to develop new methods for the synthesis of azocinoindole derivatives, we found that 2-propargyl-β-tetrahydrocarbolines can undergo ring expansion and spirocyclization under gold catalysis. DFT study revealed that the reaction starts with the intramolecular cyclization of the gold-activated 2-propargyl-β-tetrahydrocarboline with a bPES. The cyclization intermediates can not only interconvert into each other via a [1,5]-alkenyl shift, but also undergo ring expansion (through fragmentation/protodeauration mechanism) or spirocyclization (through deprotonation/protodeauration mechanism). Detailed analysis of the complex PESs for substrates with different substituents indicated that the reaction selectivity is under dynamic control if the interconversion of the intermediates is slower than the ring expansion and spirocyclization processes. Otherwise, the chemical outcome is under typical kinetic control and determined by the relative preference of ring expansion versus spirocyclization pathways. The present study may enrich chemist's understanding of the determinants for selectivities on bPESs. [ABSTRACT FROM AUTHOR]

The article explores on the impact of Morita-Baylis-Hillman carbonates with azomethine imines to the enantioselectivity of phosphine. It highlights the importance of nucleophilic phosphine-catalyzed annulation reaction to the synthesis of natural products. It cites the accessibility and stability of azomethine imines in metal-catalyzed and organocatalytic cycloadditions.

Due to the unique crystallinity of poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT), it is an excellent model polymer to study the structure--property relationship in organic devices, especially those relying on junctions of electron- and hole-transporting materials. Here, we report the synthesis and characterization of a series of monodisperse PBTTT oligothiophenes (n = 1-5) and systematically examine the evolution of crystalline behavior, morphology, and interaction with [6,6]-phenyl C61-butyric acid methyl ester (PCBM) as the molecular conjugation length increases. We discovered that fullerene intercalation occurs when there is enough free volume between the side chains to accommodate the fullerene molecule. The intercalation of PCBM is observed beyond BTTT-2 and longer oligomers, likely similar to that of PBTTT. Interestingly, both experiments and molecular simulations show that PCBM intercalation also appears to "catalyze" a more efficient packing of the BTTT-2 dimers. Crystal structure analysis revealed that the straight BTTT-2 side chains form one-dimensional (ID) channels that could perfectly host PCBM but, in the pure material, accommodate the interdigitated side chains from adjacent layers. In the blend with PCBM, these channels are maintained and enable the cocrystallization and intercalation of PCBM. This is the first time the actual sublattice cell of PCBM has been determined from the X-ray data, and demonstration the utility of the oligomers as model systems for their polymer counterparts. Among the organic photovoltaic devices (OPVs) made from the BTTT oligomers and [6,6]-phenyl C71-butyric acid methyl ester (PC71BM) blends, the ones containing the BTTT-2 dimer exhibit the highest performance. [ABSTRACT FROM AUTHOR]

Surface functionalization of an inorganic surface with bio-organic molecules is often aimed at creating a "permanent" bio-organic surface with receptor functional groups. We show here that L-cysteine can be used to transform a highly reactive Si(111)7x7 surface to not just a permanent bio-organic surface but also a semipermanent (or renewable) and a temporary bio-organic surfaces by manipulating the exposure. In the early growth stage, the strong bonding between the first cysteine adlayer and the Si substrate through Si-N or Si-S linkages in unidentate or bidentate arrangement provides permanent biofunctionalization by this interfacial layer. This interfacial layer can be used to build a transitional layer (second adlayer) mediated by interlayer vertical hydrogen bonding between an amino group and a carboxylic acid group. Further exposure of cysteine eventually leads to a zwitterionic multilayer film involving electrostatic interactions between cation (-NH3+) and anion moieties (-COO-). The interlayer hydrogen bonding therefore provides temporary trapping of bio-organic molecules as the second transitional layer that is stable up to 175 °C. This transitional layer can be easily removed by annealing above this temperature and then regenerated with the same molecular layer or a different one by "renewing" the interlayer hydrogen bonds. We also illustrate coverage-dependent adsorption structures of cysteine, from bidentate to unidentate attachments and to self-assembled multimers, involving formation of intralayer horizontal N⋯H-O hydrogen bonds, by combining our X-ray photoemission data with the local density-of-state images obtained by scanning tunnelling microscopy. [ABSTRACT FROM AUTHOR]

We report the synthesis of cobalt complexes of novel iminopyridine–oxazoline (IPO) ligands and their application to the asymmetric hydroboration of 1,1-disubstituted aryl alkenes. The new catalysts afforded α-alkyl-β-pinacolatoboranes with exclusive regioselectivity in high yields with up to 99.5% ee. Furthermore, we have applied this method to an efficient synthesis of naproxen. [ABSTRACT FROM AUTHOR]

We report the synthesis and characterization of “bistetracene”, an unconventional, linearly extended conjugated core with eight fused rings. The annellation mode of the system allows for increased stability of the conjugated system relative to linear analogues due to the increased number of Clar aromatic sextets. By attaching the appropriate solubilizing substituents, efficient molecular packing with large transfer integrals can be obtained. The electronic structure calculations suggest these large polycyclic aromatic hydrocarbons (PAHs) exhibit excellent intrinsic charge transport properties. Charge carrier mobilities as large as 6.1 cm2 V−1 s−1 and current on/off ratios of 107 were determined experimentally for one of our compounds. Our study provides valuable insight into the design of unconventional semiconductor compounds based on higher PAHs for use in high-performance devices. [ABSTRACT FROM AUTHOR]

Rhenium-catalyzed oxyalkylation of alkenes is described, where hypervalent iodine(III) reagents derived from widely occurring aliphatic carboxylic acids were used as, for the first time, not only an oxygenation source but also an alkylation source via decarboxylation. The reaction also features a wide substrate scope, totally regiospecific difunctionalization, mild reaction conditions, and ready availability of both substrates. Mechanistic studies revealed a decarboxylation/radical-addition/cation-trapping cascade operating in the reaction. [ABSTRACT FROM AUTHOR]

Developing highly active hydrodesulfurization (HDS) catalysts is of great importance for producing ultraclean fuel. Herein we report on crystalline mordenite nanofibers (NB-MOR) with a bundle structure containing parallel mesopore channels. After the introduction of cobalt and molybdenum (CoMo) species into the mesopores and micropores of NB-MOR, the NB-MOR-supported CoMo catalyst (CoMo/NB-MOR) exhibited an unprecedented high activity (99.1%) as well as very good catalyst life in the HDS of 4,6-dimethyldibenzothiophene compared with a conventional γ-alumina-supported CoMo catalyst (61.5%). The spillover hydrogen formed in the micropores migrates onto nearby active CoMo sites in the mesopores, which could be responsible for the great enhancement of the HDS activity. [ABSTRACT FROM AUTHOR]

Increasing the complexity of hollow structures, in terms of chemical composition and shell architecture, is highly desirable for both fundamental studies and realization of various functionalities. Starting with metal–organic frameworks (MOFs), we demonstrate a general approach toward the large-scale and facile synthesis of complex hollow microboxes via manipulation of the template-engaged reactions between the Prussian blue (PB) template and different alkaline substances. The reaction between PB microcubes with NaOH solution leads to the formation of Fe(OH)3 microboxes with controllable multishelled structure. In addition, PB microcubes will react with the conjugate bases of metal oxide based weak acids, generating multicompositional microboxes (Fe2O3/SnO2, Fe2O3/SiO2, Fe2O3/GeO2, Fe2O3/Al2O3, and Fe2O3/B2O3), which consist of uniformly dispersed oxides/hydroxides of iron and another designed element. Such complex hollow structures and atomically integrated multiple compositions might bring the usual physiochemical properties. As an example, we demonstrate that these complex hollow microboxes, especially the Fe2O3/SnO2 composite microboxes, exhibit remarkable electrochemical performance as anode materials for lithium ion batteries. [ABSTRACT FROM AUTHOR]

Monodispersed conjugated oligothiophenes are receiving attention in fundamental and applied science due to their interesting optical, optoelectronic, and charge transport properties. These "low molecular weight" polymers serve as model structures for the corresponding polymer analogues, which are inherently polydispersed. Here we report the synthesis, electronic structure, molecular packing/morphology, and charge transport properties of monodispersed oligothiophenes with up to six didodecylquaterthiophene (DDQT) building block repeat units (i.e., 24 thiophene units). At the point where the effective conjugation length is reached, the electronic structure showed convergence behavior to the corresponding polymer, poly(3,3″-didodecyl-quaterthiophene) (PQT-12). X-ray crystal structure analysis of the dimer (DDQT-2) showed that terminal thiophenes exhibit syn-conformations, similar to the terminal syn-conformations observed in the trimer (DDQT-3). The dimer also exhibits a rare bending of the terminal alkyl side chains in order to prevent steric hindrance with neighboring hydrogens attached to core thiophenes. Grazing incidence X-ray scattering measurements revealed a morphology evolution from small molecule-like packing to polymer-like packing in thin films, with a morphology transition occurring near the effective conjugation length. Charge transport measurements showed a mobility increase with decreasing chain length. We correlated the molecular packing and morphology to charge transport and determined that carrier mobilities are most sensitive to crystallinity and crystal grain misorientation. This indicates that molecular weight is not a decisive factor for improved carrier mobility in the low molecular weight region, but rather the degree in crystallinity and in-plane crystal orientation. These results represent a fundamental advancement in understanding the relationship between conjugation length and carrier mobilities in oligothiophene semiconductors. [ABSTRACT FROM AUTHOR]

Fe2O3 microboxes with hierarchically structured shells have been synthesized simply by annealing Prussian blue (PB) microcubes. By utilizing simultaneous oxidative decomposition of PB microcubes and crystal growth of iron oxide shells, we have demonstrated a scalable synthesis of anisotropic hollow structures with various shell architectures. When evaluated as an anode material for lithium ion batteries, the Fe2O3 microboxes with a well-defined hollow structure and hierarchical shell manifested high specific capacity (~950 mA h g-1 at 200 mA g-1) and excellent cycling performance. [ABSTRACT FROM AUTHOR]

Controlled syntheses of multicomponent metal nanocrystals (NCs) and high-index surfaces have attracted increasing attention due to the specific physical and chemical properties of such NCs. Taking advantage of copper underpotential deposition as a bridge, hexoctahedral Au-Pd alloy NCs with {hkl} facets exposed were successfully synthesized, while phase separation occurred in the absence of Cu2+ ions. The as-prepared hexoctahedral Au-Pd alloy NCs exhibited very excellent performance in terms of both formic acid electro-oxidation and methanol tolerance due to synergism between the high-index facets and the alloy. [ABSTRACT FROM AUTHOR]

Design and preparation of highly active hydrodesulfurization (HDS) catalysts is very important for the removal of air pollution. Herein, we report an extraordinarily active HDS catalyst, which is synthesized by loading of Pd on mesoporous zeolite Y (Pd/HY-M). The mesoporous zeolite Y is successfully synthesized using a water glass containing N,N-dimethyl-N-octadecyl-N-(3-triethoxysilylpropyl) ammonium [(C2H5O)3SiC3H6N(CH3)2C18H37]+ cation as a mesoscale template. Compared with mesoporous Beta and ZSM-5 supported Pd catalysts (80.0% and 73.4% for Pd/HBeta-M and Pd/HZSM-5-M, respectively) as well as commercial catalyst of γ-Al2O3 supported Pd catalyst (31.4%), Pd/HY-M catalyst exhibited very high activity in HDS of 4,6-dimethyldibenzothiophene (4,6-DM-DBT, 97.3%). The higher activity of Pd/HY-M than that of Pd/HBeta-M and Pd/HZSM-5-M is assigned to the larger micropore size of zeolite Y compared to that of Beta and ZSM-5. Theoretical simulation and adsorption experimental data show that 4,6-DM-DBT has difficulty entering the micropores of ZSM-5 and Beta zeolites, but the micropores of Y zeolite are accessible. [ABSTRACT FROM AUTHOR]

Supramolecular coordination cages provide unique restricted inner cavities that can be exploited for molecular recognition purposes and catalysis. Their syntheses often involve complex self-organization processes and rely on the identification of preorganized, kinetically stable building units that provide ligand-accessible coordination sites. Here we report a highly effective protocol for the successive buildup of symmetrical nanoscopic polyoxometalate (POM) cages. Our methodology takes advantage of a supramolecular templating effect and utilizes the structure-directing influence of octahedral {Xx(H2O)6-x} (X = Br-, Cl-; x = 2, 4, 6) assemblies that reside inside the hollow cluster shells and determine the arrangement of di- and tetranuclear vanadate units. The approach allows the preparation of a series of high-nuclearity POM cages that are characterized by {V16As8}, {V16As10}, {V20As8}, and {V24As8} core structures. In the latter cluster cage, the vanadium centers adopt a truncated octahedral topology. The formation of this Archimedean body is the direct result of the assembly of six square {V4O8} units that cap the vertices of the encapsulated Platonic {Cl6} octahedron. To the best of our knowledge, this {V24As8} cage is the largest hybrid vanadate cluster reported to date. [ABSTRACT FROM AUTHOR]

The article presents an organocatalytic stereoselective ring-opening polymerization (ROP) of lactide (LA) at low temperature using the dimeric phosphazene bases as catalyst to produce highly isotactic polylactide (PLA) stereocomplex. It inferred that dimeric phosphazene bases exhibit excellent stereocontrol for the ROP of rac-lactide because of its high basicity, steric hindrance, and high activity at low temperature. Highly isotactic polymers were due to the effective cocrystallization.

We report a quantitative analysis of the symmetry reduction phenomenon involved in the seed-mediated growth of Pd nanocrystals under dropwise addition of a precursor solution. In addition to the elimination of self-nucleation, the dropwise approach allows for the formation of a steady state for the number of precursor ions in the growth solution, which only fluctuates in a narrow range defined by experimental parameters such as the initial concentration of precursor solution and the injection rate. We can deterministically control the growth mode (symmetric vs asymmetric) of a seed by tuning these parameters to quantitatively manipulate the reaction kinetics and thus the lower and upper limits that define the steady state. We demonstrate that there exists a correlation between the growth mode and the lower limit of precursor ions in the steady state of a seed-mediated growth process. For the first few drops of precursor solution, the resultant atoms will only be deposited on a limited number of available sites on the seed if the lower limit of the steady state is below a critical value. Afterward, the deposition of atoms will be largely confined to these initially activated sites to induce symmetry reduction if atom deposition is kept at a faster rate than surface diffusion by controlling the lower limit of precursor ions in the steady state. Otherwise, the migration of atoms to other regions through surface diffusion can access other sites on the surface of a seed and thus lead to the switch of growth mode from asymmetric to symmetric. Our study suggests that symmetry reduction can only be initiated and retained by keeping the atom deposition at a rate slow enough to limit the number of initial nucleation sites on a seed but fast enough to beat the surface diffusion process. [ABSTRACT FROM AUTHOR]

The ability to control the spin-transport properties of a molecule bridging conducting electrodes is of paramount importance to molecular spintronics. Quantum interference can play an important role in allowing or forbidding electrons from passing through a system. In this work, the spin-transport properties of a polyacetylene chain bridging zigzag graphene nanoribbons (ZGNRs) are studied with nonequilibrium Green’s function calculations performed within the density functional theory framework (NEGF-DFT). ZGNR electrodes have inherent spin polarization along their edges, which causes a splitting between the properties of spin-up and spin-down electrons in these systems. Upon adding an imidazole donor group and a pyridine acceptor group to the polyacetylene chain, this causes destructive interference features in the electron transmission spectrum. Particularly, the donor group causes a large antiresonance dip in transmission at the Fermi energy EF of the electrodes. The application of a gate is investigated and found to provide control over the energy position of this feature making it possible to turn this phenomenon on and off. The current-voltage (I-V) characteristics of this system are also calculated, showing near ohmic scaling for spin-up but negative differential resistance (NDR) for spin-down. [ABSTRACT FROM AUTHOR]

The Diels–Alder (DA) reactions of pentacene (PT), 6,13-bis(2-trimethylsilylethynyl)pentacene (TMS-PT), bistetracene (BT), and 8,17-bis(2-trimethylsilylethynyl)bistetracene (TMS-BT) with the [6,6] double bond of [60]fullerene have been investigated by density functional theory calculations. Reaction barriers and free energies have been obtained to assess the effects of frameworks and substituent groups on the DA reactivity and product stability. Calculations indicate that TMS-BT is about 5 orders of magnitude less reactive than TMS-PT in the reactions with [60]fullerene. This accounts for the observed much higher stability of TIPS-BT than TIPS-PT when mixed with PCBM. Surprisingly, calculations predict that the bulky silylethynyl substituents of TMS-PT and TMS-BT have only a small influence on reaction barriers. However, the silylethynyl substituents significantly destabilize the corresponding products due to steric repulsions in the adducts. This is confirmed by experimental results here. Architectures of the polycyclic aromatic hydrocarbons (PAHs) play a crucial role in determining both the DA barrier and the adduct stability. The reactivities of different sites in various PAHs are related to the loss of aromaticity, which can be predicted using the simple Hückel molecular orbital localization energy calculations. [ABSTRACT FROM AUTHOR]

Palladium octahedra with controlled edge lengths were obtained from Pd cubes of a single size. The success of this synthesis relies on a transformation involving oxidative etching and regrowth. Because the {100} side faces of the Pd nanocubes were capped by Br– ions, Pd atoms were removed from the corners during oxidative etching, and the resultant Pd2+ ions could be reduced and deposited back onto the nanocubes, but preferentially on the {100} facets. We could control the ratio of the etching and regrowth rates (Retching and Rregrowth) simply by varying the amount of HCl added to the reaction solution. With a large amount of HCl, etching dominated the process (Retching ⪢ Rregrowth), resulting in the formation of Pd octahedra with an edge length equal to 70% of that of the cubes. In contrast, with a small amount of HCl, all of the newly formed Pd2+ ions could be quickly reduced and deposited back onto the Pd cubes. In this case, Retching ≈ Rregrowth, and the resultant Pd octahedra had roughly the same volume as the starting cubes, together with an edge length equal to 130% of that of the cubes. When the amount of HCl was between these two extremes, we obtained Pd octahedra with intermediate edge lengths. This work not only advances our understanding of oxidative etching in nanocrystal synthesis but also offers a powerful means for controlling the shape and size of metal nanocrystals simply by adjusting the rates of etching and regrowth. [ABSTRACT FROM AUTHOR]

Wiring systems powered by highly efficient superconductors have long been a dream of scientists, but researchers have faced practical challenges such as finding flexible materials. Here we report superconductivity in Nb2PdxS5-δ fibers with transition temperature up to 7.43 K, which have typical diameters of 0.3-3 μm. Superconductivity occurs in a wide range of Pd (0.6 < x <1) and S (0 < δ <0.61) contents, suggesting that the superconductivity in this system is very robust. Long fibers with suitable size provide a new route to high-power transmission cables and electronic devices. [ABSTRACT FROM AUTHOR]

We have successfully constructed a tetrahedral Ti4L6 cage with calixarene-like coordination-active vertices. It further features high solubility and stability in H2O and DMF/ H2O solution, affording an interesting stepwise assembly function with other metal ions. Through trapping of different amounts of Co or Ln ions, the Ti4L6 tetrahedra can be organized into various dimensional architectures, including a Ti4L6-Co3 cage, a Ti4L6-Ln2 cage, a Ti4L6-Ln2 chain, and a three-dimensional Ti4L6-Ln framework. An unusual mixed-valence phenomenon was observed in the Ti4L6 cage, whose Ti3+/4+ compositions were adequately identified by electron spin resonance and X-ray photoelectron spectroscopy analyses. More remarkably, the calixarene-like oxygen vertices of the Ti4L6 cage can also be used for the recognition of C3-symmetric dye molecules through N-H⋯O hydrogen bonding. Accordingly, driven by visible light, selective and efficient homogeneous photodecomposition of acid blue 93 and alkali blue 4B were successfully achieved. Therefore, this work not only represents a milestone in constructing symmetric Ti-based cages with interesting coordination assembly function but also provides a new method for preparing technologically important soluble photoactive cages. [ABSTRACT FROM AUTHOR]

The garnet-based solid state electrolyte (SSE) is considered a promising candidate to realize all solid state lithium (Li) metal batteries. However, critical issues require additional investigation before practical applications become possible, among which high interfacial impedance and low interfacial stability remain the most challenging. In this work, neutron depth profiling (NDP), a nondestructive and uniquely Li-sensitive technique, has been used to reveal the interfacial behavior of garnet SSE in contact with metallic Li through in situ monitoring of Li plating-stripping processes. The NDP measurement demonstrates predictive capabilities for diagnosing short-circuits in solid state batteries. Two types of cells, symmetric Li/garnet/Li (LGL) cells and asymmetric Li/garnet/carbonnanotubes (LGC), are fabricated to emulate the behavior of Li metal and Li-free Li metal anodes, respectively. The data imply the limitation of Li-free Li metal anode in forming reliable interfacial contacts, and strategies of excessive Li and better interfacial engineering need to be investigated. [ABSTRACT FROM AUTHOR]

Asymmetric total synthesis of structurally intriguing and highly oxygenated lancifodilactone G acetate (7) has been achieved for the first time in 28 steps from a cheap commodity chemical, 2-(triisopropylsiloxy)-1,3-butadiene. [ABSTRACT FROM AUTHOR]

A facile α-arylation of nitriles has been developed by simply introducing Tf2O and DABCO to the mixture of nitriles and aryl sulfoxides. The transformation consists of two sequential steps: (i) Tf2O-initiated electrophilic assembly and and (ii) DABCO-triggered rearrangement. Each step can be tuned independently by changing the temperature and/or base. This adjustability allows the method to accommodate a wide range of substrates. Notable features of this new protocol include remarkable efficiency (20 min, -30 °C), exclusive regioselectivity, and high functional group compatibility, which can be challenging issues in traditional approaches. NMR studies not only identified a unique, highly unstable sulfonium imine complex but also demonstrated the importance of temperature in the formation and manipulation of this key intermediate. Further DFT calculations suggested that an electrophilic assembly, followed by removal of HOTf (by base), and finally [3,3]-sigmatropic rearrangement are three key stages in the reaction. The versatile transformability of the products and easy scalability of this reaction are also exhibited here. [ABSTRACT FROM AUTHOR]

Metallic nanotubes represent a class of hollow nanostructures with unique catalytic properties. However, the wet-chemical synthesis of metallic nanotubes remains a substantial challenge, especially for those with dimensions below 50 nm. This communication describes a simultaneous alloying-etching strategy for the synthesis of Pt nanotubes with open ends by selective etching Au core from coaxial Au/Pt nanorods. This approach can be extended for the preparation of Pt nanorings when Saturnlike Au core/Pt shell nanoparticles are used. The diameter and wall thickness of both nanotubes and nanorings can be readily controlled in the range of 14--37 nm and 2--32 nm, respectively. We further demonstrated that the nanotubes with ultrathin side walls showed superior catalytic performance in oxygen reduction reaction. [ABSTRACT FROM AUTHOR]

We present the formation of the largest titanium-oxo cluster, [Ti42(μ3-O)60(OiPr)42(OH)12)]6-, with the first fullerene-like Ti-O shell structure. The {Ti42O60} core of this compound exemplifies the same icosahedral (Ih) symmetry as C60, the highest possible symmetry for molecules. According to the coordination environments, the Ti centers in this cluster can be arranged into a Platonic {Ti12} icosahedron and an Archimedean {Ti30} icosidodecahedron. The solution stability of this cluster was confirmed by electrospray ionization mass spectrometry. The spherical body of the {Ti42O60} core has an inside diameter of 1.05 nm and an outside diameter of 1.53 nm, which could be directly visualized by high-resolution transmission electron microscopy. Our results demonstrate that titanium oxide can also form fullerene-like shell structures. [ABSTRACT FROM AUTHOR]

Reported herein is a series of Ru2(Xap)4 capped polyyn-diyl compounds, where Xap is either 2-anilinopyridinate (ap) or its aniline substituted derivatives. Symmetric [Ru2(Xap)4](μC4t)[Ru2(Xap)4] (compounds 4ka (X = 3-isobutoxy) and 4kc (X = 3,5-dimethoxy) with k = 2, 3, 4, and 5) was obtained from the Glaser “4 coupling reaction of Ru2(Xap)4(C2k.H). Unsymmetric [Ru2(Xap)4]- (μ-C4k+2)[Ru2(Xap)4] (compounds 4k+2b with k = 2, 3, and 4) were prepared from the Glaser coupling reaction between Ru2(Xap)4(C2k+2H) and Ru2(Xap)4(C2kH). X-ray diffraction study of compound 12c revealed both the sigmoidal topology of the polyyndiyl bridge and the fine structural detail about the Ru2 cores.Cyclic and differential pulse voltammetric (CV and DPV) measurements and spectroelectrochemical studies revealed that (i) the reduced monoanions [Ru2—C2m—Ru2]-1 (m = 4—8) belong to the Robin-Day class II mixed valent ions and (ii) the electronic coupling between Ru2 termini depends on the length of the polyyn-diyl bridge with an attenuation constant (γ) between 0.12 and 0.15 Å-1. In addition, spin-unrestricted DFT calculations provide insight about the nature of orbitals that mediate the long distance electronic coupling. [ABSTRACT FROM AUTHOR]

Ultrathin crystalline nanosheets give an extremely high surface area of a specific crystal facet with unique physical and chemical properties compared with normal three-dimensionally polyhedral nanocrystals (NCs). However, the ultrathin metal nanosheets tend to curl themselves or assemble with each other sheet by sheet, which may reduce the effective surface area and accordingly the catalytic activity to a great extent. Here we report a facile wet-chemical route that allows the fabrication of novel excavated rhombic dodecahedral (ERD) PtCu3 alloy NCs with ultrathin nanosheets of high-energy {110} facets. The surface area was measured to be 77 m² g-1 by CO stripping, although the particle size is about 50 nm. Electrochemical characterizations showed that the ERD PtCu3 NCs exhibit excellent electrocatalytic performance and high antipoisoning activity in comparison with commercial Pt black andPtCu3 alloy NCs with {111} surfaces. [ABSTRACT FROM AUTHOR]

The first metal-catalyzed [6 + 3] cycloaddition of tropone with azomethine ylides has been developed. With the use of a chiral ferrocenylphosphine-copper(I) complex as the catalyst, the asymmetric variant of the [6 + 3] cycloaddition has also been successfully achieved. The reactions proceeded smoothly under mild conditions, affording piperidine-fused bicyclic heterocycles in moderate to high yields with good to excellent diastereo- and enantioselectivies. The procedures are operationally simple and the catalysts are cheap and readily accessible, thus providing a practical approach to piperidine-fused bicyclic heterocycles. [ABSTRACT FROM AUTHOR]

We investigated the structure–morphology–performance relationship of diketopyrrolopyrrole (DPP)-based low band gap polymers with different donor cores in organic field effect transistors (OFETs) and organic photovoltaics (OPVs). The change in the chemical structure led to strong physical property differences, such as crystalline behavior, blend morphology, and device performance. In addition, the choice of solvents and additives enabled one to fine tune the properties of these materials in the condensed state. For instance, when thin films were processed from solvent mixtures, both in the pure polymer and in a blend, we observed an enhanced edge-on orientation and the formation of thinner and longer polymer fibrils. In the BHJ blends, processing from a solvent mixture reduced the size scale of the phase separation and promoted the formation of a fibrillar network morphology, having a polymer–PCBM mixture filling the interfibrillar regions. The characteristic length scale of the fibrillar network dictated the specific inner surface area, which directly correlated to the performance in the OPV devices. When the BHJ mixture was processed from a single solvent, a large-scale phase separated morphology was observed that was stratified, normal to the film surface. A strong scattering anisotropy was observed in the resonant soft X-ray scattering of the blends that provided insight into the packing of the polymer chains within the fibrils. The morphology and performance trend in OPVs paralleled the performance in an OFET, suggesting that similar processing conditions should be considered in OFET fabrication. [ABSTRACT FROM AUTHOR]

A series of new pincer iron complexes with electron-donating phosphinite-iminopyridine (PNN) ligands has been prepared and characterized. These iron compounds are efficient and selective catalysts for the anti-Markovnikov alkene hydrosilylation of primary, secondary, and tertiary silanes. More importantly, the system exhibits unprecedented functional group tolerance with reactive groups such as ketones, esters, and amides. Furthermore, the iron-catalyzed alkene hydrosilylation was successfully applied to the synthesis of a valuable insecticide, silafluofen. The electronic properties and structures of the iron complexes have been studied by spectroscopies and computational methods. Overall, the iron catalysts may provide a low-cost and environmentally benign alternative to currently employed precious metal systems for alkene hydrosilylation. [ABSTRACT FROM AUTHOR]

The self-assembly of well-defined 2D supramolecular polymers in solution has been a challenge in supramolecular chemistry. We have designed and synthesized a rigid stacking-forbidden 1,3,5-triphenylbenzene compound that bears three 4,4'-bipyridin-1-ium (BP) units on the peripheral benzene rings. Three hydrophilic bis(2-hydroxyethyl)carbamoyl groups are introduced to the central benzene ring to suppress 1D stacking of the triangular backbone and to ensure solubility in water. Mixing the triangular preorganized molecule with cucurbit[8]uril (CB[8]) in a 2:3 molar ratio in water leads to the formation of the first solution-phase single-layer 2D supramolecular organic framework, which is stabilized by the strong complexation of CB[8] with two BP units of adjacent molecules. The periodic honeycomb 2D framework has been characterized by various 1H NMR spectroscopy, dynamic light scattering, X-ray diffraction and scattering, scanning probe and electron microscope techniques and by comparing with the self-assembled structures of the control systems. [ABSTRACT FROM AUTHOR]

We have investigated two alternative mechanisms for the ring-opening polymerization of L-lactide using a guanidine-based catalyst, the first involving acetyl transfer to the catalyst, and the second involving only hydrogen bonding to the catalyst. Using computational chemistry methods, we show that the hydrogen bonding pathway is considerably preferred over the acetyl transfer pathway and that this is consistent with experimental information. [ABSTRACT FROM AUTHOR]

Examines the transition metal-catalyzed cycloaddition reactions. Effect of rhodium catalyst on the cycloaddition; Optimization analysis of hexynone; Appropriate temperature for the reaction.