A spectrochemometric approach to tautomerism and hydrogen-bonding in 3-acyltetronic acids

3-Acyltetronic acids bearing different 3- and 5-substituents have been examined focussing on tautomerism and inter- and intramolecular hydrogen-bonding properties of these ß,ß'-tricarbonyl compounds in solution as well as in the solid state. Spectroscopic methods like NMR, IR, Raman-spectroscopy as well as X-ray diffractometry and MAS-NMR for the solid state have been applied. In a solution of CDCl3, the acids exist as cis/trans pair both involving the 3-acyl group in a ratio 60/40. The pair also involving the carbonyl group at C-4 is tautomeric and the most abundant, whereas the other isomer only shows one form with an exo-cyclic double bond. NMR and IR measurements are in agreement. In the solid state, only one of the four possible tautomers is found. DFT-calculations on the B3LYP/6-31G** level helped to verify the assignment of the IR- and NMR-spectra and yielded an estimation of the relative thermodynamic stabilities of the tautomers of several 3-acyltetronic acids. Low temperature NMR experiments gave an insight into the equilibria. Deuterium isotope effects on the 13C NMR chemical shifts have been observed for 5,5-dimethyl 3-pivaloyltetronic acid at low temperature in order to examine the fast internal equilibria

Influence of domain size on optical properties of ordered GaInP₂

Using dark‐field transmission electron microscopy images of ordered GaInP samples, we show how the ordering domain size depends on the growth temperature. Samples with different average domain sizes are compared with regard to their photoluminescence (PL) and excitation spectra. We find a close correlation between the size of the ordered domains and the relative intensity of the PL peak from band–band recombination compared with the rapidly shifting, below‐band‐gap luminescence emission

Real-Time Visualization of Convective Transportation of Solid Materials at Nanoscale

Convective transportation of materials in the solid state occurring in a prototype solid bilayer system of Al and Si with negligible mutual solubility has been directly imaged in real time at nanoscale using a valence energy-filtered transmission electron microscope. Such solid-state convection is driven by the stress gradient developing in the bilayer system due to the amorphous to crystalline phase transformation of the Si sublayer. The process is characterized by compression experienced in the Si phase crystallizing within the Al sublayer, as well as by the development of mushroom-shaped “plumes” of Al nanocrystals in the Si sublayer as a result of compressive stress relaxation and discrete, new nucleation of crystalline Al. The real-time, atomistic observation and the thus-obtained fundamental understanding of solid-state convection enable highly sophisticated applications of such a complex process in advanced fabrication and processing of nanomaterials and solid-state devices

Eleven Nanometer Alignment Precision of a Plasmonic Nanoantenna with a Self-Assembled GaAs Quantum Dot

Plasmonics offers the opportunity of tailoring the interaction of light with single quantum emitters. However, the strong field localization of plasmons requires spatial fabrication accuracy far beyond what is required for other nanophotonic technologies. Furthermore, this accuracy has to be achieved across different fabrication processes to combine quantum emitters and plasmonics. We demonstrate a solution to this critical problem by controlled positioning of plasmonic nanoantennas with an accuracy of 11 nm next to single self-assembled GaAs semiconductor quantum dots, whose position can be determined with nanometer precision. These dots do not suffer from blinking or bleaching or from random orientation of the transition dipole moment as colloidal nanocrystals do. Our method introduces flexible fabrication of arbitrary nanostructures coupled to single-photon sources in a controllable and scalable fashion