Atom-scale ptychographic electron diffractive imaging of boron nitride cones

Ptychographic coherent diffractive imaging (CDI) has been extensively applied using both x rays and electrons. The extension to atomic resolution has been elusive. This Letter demonstrates ptychographic electron diffractive imaging at atomic resolution, permitting identification of structure in a boron nitride helical cone at a resolution of order 1 ?, beyond that of comparative Z-contrast images. A scanning transmission electron microscope is used to create a diverging illumination in a defocused Fresnel CDI geometry, providing a robust strategy leading to a unique solution.     

Synthesis of novel thieno[3,2-b]thienobis(silolothiophene) based low bandgap polymers for organic photovoltaics

Thieno[3,2-b]thienobis(silolothiophene), a new electron rich hexacyclic monomer has been synthesized and incorporated into three novel donor-acceptor low-bandgap polymers. By carefully choosing the acceptor co-monomer, the energy levels of the polymers could be modulated and high power conversion efficiencies of 5.52% were reached in OPV devices.     

100 Picosecond Diffraction Catches Structural Transients of Laser‐Pulse Triggered Switching in a Spin‐Crossover Crystal

We study by 100 picosecond X‐ray diffraction the photo‐switching dynamics of single crystal of the orthorhombic polymorph of the spin‐crossover complex [(TPA)Fe(TCC)]PF₆, in which TPA=tris(2‐pyridyl methyl)amine, TCC^2?=3,4,5,6‐Cl₄‐Catecholate^2?. In the frame of the emerging field of dynamical structural science, this is made possible by using optical pump/X‐ray probe techniques, which allow following in real time structural reorganization at intra‐ and intermolecular levels associated with the change of spin state in the crystal. We use here the time structure of the synchrotron radiation generating 100 picosecond X‐ray pulses, coupled to 100 fs laser excitation. This study has revealed a rich variety of structural reorganizations, associated with the different steps of the dynamical process. Three consecutive regimes are evidenced in the time domain: 1) local molecular photo‐switching with structural reorganization at constant volume, 2) volume relaxation with inhomogeneous distribution of local temperatures, 3) homogenization of the crystal in the transient state 100 µs after laser excitation. These findings are fundamentally different from those of conventional diffraction studies of long‐lived photoinduced high spin states. The time‐resolution used here with picosecond X‐ray diffraction probes different physical quantities on their intrinsic time‐scale, shedding new light on the successive processes driving macroscopic switching in a functionalized material. These results pave the way for structural studies away from equilibrium and represent a first step toward femtosecond crystallography.     

Formation of Quaternary Stereogenic Centers by NHC–Cu‐Catalyzed Asymmetric Conjugate Addition Reactions with Grignard Reagents on Polyconjugated Cyclic Enones

The copper‐catalyzed conjugate addition of various Grignard reagents to polyconjugated enones (dienone and enynone derivatives) is reported. The catalyst system, composed of copper triflate and an NHC ligand, led to the unusual selective formation of the 1,4‐addition products. This reaction allows for the creation of all‐carbon chiral quaternary centers with enantiomeric excesses up to 99 %. The remaining unsaturation on the 1,4 adducts give access to valuable synthetic transformations.     

Experimental evidence and DFT studies of next-nearest-neighbor magnetic interactions through diamagnetic 3d and 4d ions

The copper template effect allows the preparation of tridentate ligands that chelate copper ions, leaving unoccupied the fourth basal coordination position and at least one axial position of the copper coordination polyhedron. Two such cationic complexes, [LCu](+) and [L(1)Cu](+) (L(-) = 2-{(E)-[(2-aminoethyl)imino]methyl}phenoxo] and L(1-) = 2-{(E)-[(2-aminopropyl)imino]methyl}phenoxo), react with diamagnetic polycyanometalate tectons such as Ni(CN)(4)(2-) or Ag(CN)(2)(-) to yield different neutral 1D complexes. In {[(LCu)(2)Ni(CN)(4)]}(n) (1) the four cyano nitrogen atoms are involved in coordination with copper ions in such a manner that each copper atom is pentacoordinated and linked to two cyano functions that occupy axial and equatorial coordination positions. Two L(1)Cu(+) cationic entities are linked, through their equatorial plane, to two trans cyano groups of the Ni(CN)(4)(2-) tecton in complex [(L(1)Cu)(2)Ni(CN)(4)] (2), the two uncoordinated cyano groups being involved in hydrogen bonds. 2 is a racemate, a S stereoisomer being associated with a R one in each [(L(1)Cu)(2)Ni(CN)(4)] unit. Zigzag Cu-Ag chains are present in [(LCu)Ag(CN)(2)] (3), where the copper centers are pentacoordinated and connected to the cyano groups in an alternate axial-equatorial coordination scheme. A bidimensional structure is developed by interchain argentophilic interactions. In complex 4, {(L(1)CuMeOH)(L(1)Cu)[Ag(CN)(2)](2)}, two L(1)Cu units are connected by a NC-Ag-CN bridge in an equatorial position. These resulting units exhibit argentophilic interactions with [Ag(CN(2))](-) entities that are monocoordinated in the equatorial position to the next unit, ultimately leading to a chain. Weak Cu-Cu magnetic interactions are detected in the four compounds, antiferromagnetic in the case of equatorial-equatorial copper interactions, ferromagnetic for orthogonal interacting copper orbitals (axial-equatorial interactions), while axial-axial bridges are characterized by an absence of interaction. The presence of weak ferromagnetic interactions through large NC-Ni-CN or NC-Ag-CN bridges (Cu···Cu distances larger than 10 ?) furnishes experimental evidence for the existence of next-nearest-neighbor interactions through diamagnetic centers. DFT calculations do confirm the existence of these magnetic transmission pathways through the diamagnetic metal bridge.     

Further numerical methods for the Falkner-Skan equations: Shooting and continuation techniques

We consider in this paper the numerical solution of the Falkner-Skan differential equation, modelling under some similarity assumptions the boundary layer equation. We look for the extremal solution of this third order differential equation. The methods we use are basically the Newton method with a shooting process, which is coupled with a continuation method: they allow us to follow the solution arcs which contain regular and turning point solutions.     

X-ray diffraction,differential scanning calorimetric and spectroscopic studies of phase transitions in the bidimensional compound (C12H25NH3)2CdCl4

The existence of three main crystalline phases (called III, II and I) in (C₁₂H₂₅NH₃)₂CdCl₄ has been revealed by differential scanning calorimetry. X-ray diffraction and spectroscopic studies. The crystal- lographic evolution with increasing temperature appears to be monoclinic (III) → orthorhombic (II) → tetragonal (I). The low temperature phase III is the only ordered structure. The phase transition (III-II), which is of first order type, corresponds to an order-disorder mechanism involving the organic part of the structure (alkylammonium chains) whereas the phase transition (II-I), which is of second-order type, is related to the arrangement of the mineral matrix (octahedra of perovskite layers). An intermediate disordered form II', stable in a very narrow temperature range and structurally similar to the form II, has also been observed, so that the transformation (III-II) proceeds, in fact, in two steps (III-II'-II). The variation enthalpies observed at the transitions (III-II'-II) and analyzed through an order-disorder mechanism demonstrate the high disorder of the alkylammonium chains in form II, in agreement with spectroscopic results. No thermal anomaly or spectroscopic modification is observed for the high temperature transition (II-I).     

Thermodynamic analysis of the phase separation during the polymerization of a thermoset system into a thermoplastic matrix. II. Prediction of the phase composition and the volume fraction of the dispersed phase

A thermodynamic simulation of the phase‐separation process of an off‐critical blend, based on a thermoplastic matrix with a reactive epoxy system undergoing polycondensation at a constant temperature, was performed. The model considered the composition dependence of the interaction parameter, χ(T,Φ₂) (where T is the temperature and Φ₂ is the volume fraction of polystyrene), along with the polydispersity of both polymers. For every level of conversion, the simulation provided the amount, composition, stoichiometric ratio, and conversion of each phase present. The accuracy of the model was proved by the good agreement between the experimental and predicted glass‐transition temperatures and heat capacity changes at the glass‐transition temperatures for both phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1361–1368, 2004     

Porous Ionic Liquids or Liquid Metal–Organic Frameworks?

Porous liquids can be prepared from the dispersion metal–organic frameworks (MOFs) in ionic liquids (ILs). Porous liquids prepared from 5 % of ZIF‐8 in a phosphonium‐based ionic liquid are capable of absorbing reversibly up to 150 % more nitrogen and 100 % more methane than the pure ionic liquid.