Synthesis and photodimerisation of tetrabenzo[ab,f,jk,o][18]annulenes

Abstract The tetrabenzo[ab,f,jk,o][18]annulenes 7a,b, generated in a 5-step synthesis, show photodimerisation and -oligomerisation reactions in the solid state and in solution. The state of aggregation determines the reaction route. Whereas the cyclodimer 8a has a simple cyclobutane structure, the dimer 8b is a highly symmetrical cyclophane.

ChemInform Abstract: Synthesis and Photodimerization of Tetrabenzo[ab,f,jk,o][18]annulenes.

Comparison of electron diffraction data from non-linear optically active organic DMABC crystals obtained at 100 and 300 kV

During the recent past, we have synthesized a new class of molecules with intramolecular two-dimensional charge transfer upon excitation. The present report presents such a molecule, 2,6-bis(4-dimethylamino-benzylidene)-cyclohexanone (DMABC), with an unusually high value of the second-order non-linear optical (NLO) coefficients. In order to optimize the macroscopic NLO properties of the compounds, it is necessary to relate their first hyperpolarizability tensors at a molecular level to those at a crystal bulk level. This requires a complete structure determination and refinement. However, the growth of sufficiently large single crystals, which are needed for structural analysis and refineme…

Strategies for structure solution and refinement of small organic molecules from electron diffraction data and limitations of the simulation approach

In recent years, a series of non-linear optically active bis(benzylidene) ketones have been synthesized and investigated by electron crystallography. In most cases, structure refinement was possible by combining electron diffraction analysis and quantum-mechanical calculations with maximum-entropy methods. However, when the torsional angles between the phenyl rings and the C=C double bonds are strongly affected by the crystal field, this method fails because packing-energy calculations are not sufficiently sensitive. This problem can be solved by refining the approximate model with SHELXL, if the data set is sufficiently accurate and the model close to the correct structure. Here it is show…

Studies of structures and properties of polymeric systems containing bis-(hydroxy-arylidene)alkanones as NLO-active chromophores

Abstract NLO-properties of polymer systems containing bis-(hydroxy-arylidene)alkanone chromophores were studied experimentally and analyzed using ab initio quantum chemical calculations. A monoclinic crystal structure (space group P2111) of the polyester containing fragments of such chromophores in the backbone was simulated and a reasonable agreement between the experimental and simulated X-ray powder diffraction patterns was achieved. Ab initio quantum-mechanical estimations of the SHG-observable macroscopic second-order non-linearity tensor coefficients, obtained for the polymer crystal structure at the HF SCF level, led to the major dXZZ-coefficient of 1.9 pm/V. Films of ionic complexes…