The benzils 3 22 and 5 23 were prepared by oxidation of the corresponding benzoins following described procedures. The benzil 4 was synthesized via a bromination-hydrolysis sequence from 4,5diphenylimidazolin-2-one. 24 The starting benzoins were prepared from the corresponding benzaldehydes via cyanide catalyzed benzoin condensations. 23,25,26 Crystals suitable for X-ray investigations were obtained by slow evaporation of solutions of the compounds in chloroform (3), ethyl acetate-DMSO-DMF (1:1:1, v/v/v) (4), and p-xylene (5).

Being aimed at a new type of porous solids, a moduled design strategy of molecular tectons, making use of the conjugation between a shape defined artificial backbone and the bioinspired molecular fragments of nucleobases or nucleobase derivatives as functional end-caps, has been developed. This led to the formation of the new hybrid compounds 1-13 of linear and tetrahedral geometry, containing uracil, adenine, adenosine, guanosine and its acylated analogs as the sticky end-cap sites. The compounds were synthesized from a halogen or ethynyl substituted nucleobase component and the corresponding ethynylated spacer unit following a metal assisted coupling process as the key reaction step. X-Ray crystal structure analysis demonstrates that the parent compound 1 is a solvent complex with DMSO (1:2), showing the DMSO molecules incorporated in a hydrogen bonded layer structure. Specific dependencies of the fluorescence properties of the new compounds in solution on the structure of the molecules are reported. A selection of solid compounds has been studied in respect of their ability to adsorb organic vapours. They revealed significant differences both in the sorption capacity and the selectivity towards particular solvent vapours.

A series of halogenated nucleobase derivatives 1-4 is reported to yield solvent-free (2) and DMSO solvated crystals (1, 3, 4) on the crystallization from DMSO with one of them (4) containing an additional molecule of water. The molecular and crystal structures are described and comparatively discussed with reference to previous results on related compounds. The molecule of 1 is planar, molecules of 2 and 3 show syn alignment with reference to the heterocyclic ring and common C2 0 -endo conformation of the ribose residue, while 4 is also syn aligned but C4 0 -exo in the sugar conformation. The packing structures reveal typical aggregations created via networks of hydrogen bonds. These involve conventional N-HÁÁÁN, N-HÁÁÁO and O-HÁÁÁO interactions between nucleobase and ribose units as well as solvent molecules, additionally supported by weak C-HÁÁÁO contacts but excluding the participation of halogenÁÁÁhalogen interactions as well as halogenÁÁÁheteroatom contacts in the supramolecular structure formation.

Four new azulene derivatives featuring two π‐conjugated and sulfur terminated rigid side arms in the 1,3‐positions of the azulene core were designed, synthesized, and characterized. The syntheses were carried out on the basis of a palladium cross‐coupling procedure in the key reaction step. The crystal structures of the target compound 3 and of the intermediate compounds 7 and 9 have been studied. Supporting density functional theory calculations reveal insights into the electronic properties of the particular azulenes. The comparison of measured UV–Vis, infrared, and Raman data to calculated values allowed assignment of major spectral features to the particular structural differences of the new compounds and comparison to plain azulene. Cyclic voltammetry measurements were performed showing the redox characteristics of the new azulene derivatives. Copyright © 2012 John Wiley & Sons, Ltd.

† Electronic supplementary information (ESI) available: Representations of the acetone disorder and packing structure of 1a (Fig. S1) as well as 13 C and 1 H NMR data of 1 in CDCl 3 at T = 295 K (Tables S1 and S2). Crystallographic information files (CIF) have been deposited at the CCDC with the reference numbers 787340, 787341 and 870204. For ESI see DOI: xxx xxx A rather easy structured permethylated dinitro calix[4]arene was found to exhibit large, stable and rigid channels in the solid state. These were obtained as guest free as well as solvent filled species and proved to reversibly adsorb selected organic solvents. Combined use of QMB measurements and X-ray powder diffraction revealed the predominantly reversible interaction of dichloromethane vapour with the channel structure as well as the integrity of the nanopores during adsorption and desorption. Examination of the flexible host component by NMR spectroscopy revealed a mixture of interchanging conformational isomers which could explain the high sensitivity of the crystallization process from the employed solvents.