Aromatic and Antiaromatic Pathways in Triphyrin(2.1.1) Annelated with Benzo[b]heterocycles

It is important to understand the aromatic properties and magnetically induced current densities of highly conjugated chromophores when one designs molecules with strongly delocalized electronic structure. The aromatic character can be modified by linearly extending the electron delocalization pathway of the triphyrin(2.1.1) skeleton with an annelated benzo[b]heterocycle fragment. Two-electron reduction of the extended triphyrin leads to an antiaromatic triphyrin(2.1.1) ring and an aromatic benzo[b]heterocycle subunit. Detailed information about the observed pathways and their strengths are obtained by performing current-density calculation.Peer reviewe

Multiscale materials design of hard coatings for improved fracture resistance and thermal stability

Physical vapor deposited hard coatings comprised of cubic (c) transition metal (TM)-Al-N, and (TM)-Si-N are the current work horse materials for a large number of metal cutting and wear resistant applicatíons to light against the extreme conditions of temperature and stress simultaneously. In spite of a high degree of sophisticatíon in terms of material choice and microstructural design, a lower fracture resistance and limited thermal stability of the coatings remains a technological challenge in the field. The lower fracture resistance ofthe coating is an inherent material property. Limited thermal stability in the TM-Al-N system is associated with the transformation of metastable c -AIN to its stable wurtzite (w)-AIN phase ata temperature above 900 oC resulting an undesirable hardness drop. The current work shows how to overcome these challenges by manipulaling the coating material at different length scales, i.e. microstructure, crystal and interface structure, and alloy design. The endeavor of multiscale materials design is achieved by converging a deeper material and process knowledge to result specific structural modification over multiple length scales by alloying transition metal nitrides with AIN and SiNxs following. Microstructure variation is achieved in ZrN coating by alloying it with SiNx, where the surface segregated SiNx breaks down the columnar structure and evolves a self-organized nanocomposite structure with a hardness variation from 37 ±2 GPa to 26 ±1 GPa. The indentation induced fracture studies reveal crack deflection for the colum nar coating, likely a long the coiumn boundaries. The crack deflection olfers additional energy dissipative mechanisms that make the columnar structured coating more fracture resistant, which is not the case fur the nanocomposite coating in spite of its lower hardness. Crystal structure of AIN is variad between stable wurtzite structure to metastable cubic structure in the ZrAIN alloy by adapting a mullilayer structure and tuning the layerthickness. The multilayer consisting c-AIN layer shows a hardness of 34 ±1 GPa anda twofold enhancement in the critica! force to cause an indentation induced surface crack compared to the multilayer containing w-AIN in spite of a lower hardness for the later case. The higher fracture resistance is discovered to be ca u sed by stress- induced transformation of /IJN from its metastable cubic structure to its thermodynamically stable wurtzite structure associated with a molar volume expansion of20% that builds up local compressive stress zones delay;ng the onset and propagation of the cracks. This is in fact the first experím en tal data point for the stress-induced transfurmation toughening in a hard coatíng. The current work also demonstrates a concept of im proving the thermal stabilíty ofTM-Al-N by m odifying the interface structure between w-AIN and c-TMN. A popular belief in the field is that AIN in lis stable wurtzite structure is detrimental to coating hardness, and hence the curren! material design strategy Is to force AIN in metas table cubic phase that confines the application temperature (- 900 oC). In contrast, here it is shown that the w-AIN offers a high hardness provided if it is grown (semi-)coherent to c-TMN. This is experimentally shown for lhe multilayer system ofTiN/ZrAIN. The interface structure between the c-TiN, c-ZrN and w-AIN is transformed from incoherent to (semi-)coherent structure bytuning the growth conditions under a favorable crystallographic template. Furthennore, the low energy(semi-) coherent interface structure between w-AIN and c- TiN, c- ZrN display a high thermal stability, causing a high and more stable hardness up to an annealing temperature of 1150 oC with a value of34± 1.5 GPa. This value is 50 % higher comparad to the state-of-the-art monolithic and multilayered Ti-/IJ -N and Zr-Al-N coating containing incoherent w-AIN. Finally, an entropy based alloy design concept is explorad to form a thermodynamicLos recubrimientos duros formados por metales de transición (TM) cúbicos -AlN, y -SiN depositados mediante fase de vapor (CVD) son materiales extensamente utilizados en gran número de aplicaciones de corte y de desgaste bajo condiciones extremas de temperatura y solicitaciones mecánicas. A pesar de un alto grado de sofisticación en cuanto a la selección del material y el diseño microestructural, la baja resistencia a la fractura y la limitada estabilidad térmica sigue siendo un importante reto tecnológico. La variación microestructural en los recubrimientos de ZrN se controla mediante la aleación con SiNx, ya que la segregación superficial de SiNx rompe la estructura columnar y evoluciona a un nanocompuesto autoorganizado con una dureza de entre 37 ±2 GPa y 26 ±1 GPa. Las grietas producidas por indentación muestran la existencia de deflexión de grieta, lo que proporciona un mecanismo de disipación de energía adicional, haciendo de este material más resistente a la generación de grieta.La estructura cristalina del recubrimiento de AlN se varía entre la fase estable wurtzita y la fase cúbica estable ZrAlN mediante el control de la estructura y el espesor de la arquitectura multicapa. El recubrimiento multicapa formado por la fase c-AlN presenta una dureza de 34 ±1 GPa y una resistencia a la generación de grietas por indentación dos veces mayor comparado con el recubrimiento multicapa formado por w-AlN, aunque éste presente una dureza menor. La mayor resistencia a fractura está causada por la transformación inducida por tensión de AlN desde la fase cúbica metaestable a la fase wurtzita termodinámicamente estable acompañada de una expansión molar del 20%, resultando en una generación de tensiones compresivas que retarda la generación y propagación de grietas. Esta es la primera vez que se reporta la existencia de transformación catalizada por tensión en recubrimientos duros. En esta tesis también se demuestra el concepto de mejorar la estabilidad térmica de los recubrimientos basados en TM-Al-N mediante la modificación de la estructura interfacial entre las fases w-AlN y c-TMN. En general la existencia de AlN en su fase estable wurtzita puede ser detrimental para la dureza, y por lo tanto se suele depositar el material en la fase cúbica, lo que limita la temperatura de utilización (~ 900 oC). Esta dureza es un 50%mayor de la dureza reportada para recubrimientos monolíticos y multicapas de Ti-Al-N y Zr-Al-N que contengan fase incoherente de w-AlN. Finalmente, el concepto de aleaciones de alta entropía se utiliza para depositar una solución sólida termodinámicamente estable del sistema TM-Al-N que presenta una entalpía de mezcla positiva. Elementos de aleación multi-principales de (AlTiVCrNb)N se utilizan para formar una solución sólida cúbica . La alta entropía configuracional en la mezcla es mayor que la entalpía, por lo que se espera una formación de solución sólida estabilizada a temperaturas mayores de 1000K. Sin embargo, a temperaturas elevadas, la optimización entre la minimización de la energía de interacción y la maximización del desorden configuracional causa la precipitación de AlN en su estructura wurtzita estable, y la solución sólida cúbica está únicamente confinada entre TiN, CrN , VN y NbN que tienen baja entalpía de mezcla. En resumen, esta tesis presenta soluciones tecnológica a dos retos importantes en el campo. Se consigue una mejora significativa en la resistencia a fractura en los recubrimientos mediante la selección de materiales y el diseño microestructural mediante mecanismos de deflexión de grieta y transformación de fase asistida por tensión. Así mismo, se aumenta la estabilidad térmica de recubrimientos TM-Al-N mediante una nueva microestructura consistente en c-TMN y w-AlN termodinámicamente estable con una estructura interfacial (semi-)coherente de baja energía

Fully conjugated [4] chrysaorene. Redox-coupled anion binding in a tetraradicaloid macrocycle

[4]Chrysaorene, a fully conjugated carbocyclic coronoid, is shown to be a low-bandgap π-conjugated system with a distinct open-shell character. The system shows good chemical stability and can be oxidized to well-defined radical cation and dication states. The cavity of [4]chrysaorene acts as an anion receptor toward halide ions with a particular selectivity toward iodides (Ka = 207 ± 6 M–1). The interplay between anion binding and redox chemistry is demonstrated using a 1H NMR analysis in solution. In particular, a well-resolved, paramagnetically shifted spectrum of the [4]chrysaorene radical cation is observed, providing evidence for the inner binding of the iodide. The radical cation–iodide adduct can be generated in thin solid films of [4] chrysaorene by simple exposure to diiodine vapor

The phenology of winter rye in Poland: an analysis of long-term experimental data

The study of the phenology of crops, although quite popular, has limitations, mainly because of frequent changes to crop varieties and management practices. Here, we present data on the phenology and yield of winter rye in western Poland collected between 1957 and 2012 from a long-term field experiment. Data were examined for trends through time and compared to climatological factors using regression analysis. Both annual air temperature and precipitation increased during the study period, equivalent to 2 °C and 186 mm, respectively, over the 52-year period for which met data were available. We detected significant delays in sowing date and recently in emergence, but significant advances were apparent in full flowering date equivalent to 4 days/decade. Yield and plant density experienced a step like change in 1986; yield increasing by ca. 70 % and plant density increasing by ca. 50 %, almost coinciding with a similar change in annual mean temperature, but most likely caused by a changed seed rate and use of herbicides. Future climate change is expected to have a greater impact on this crop, but farmers may be able to adapt to these changes by modifying water regimes, using new machinery and sowing new rye varieties