Argentivorous molecules with chromophores: dependence of their fluorescence intensities on the distance between a donor and an acceptor.

We have prepared new argentivorous molecules (L2 and L3) having different linker lengths between cyclen and anthracene units. The structures of Ag+ complexes with the new ligands were investigated in solution and solid states. The silver(I) ion-induced 1H NMR and UV-vis spectral changes of L2 and L3 showed the presence of 1 : 1 complexes. The solid-state structures of the Ag+ complexes with L2 and L3 are stable 1 : 1 complexes because four aromatic side-arms wrap the Ag+ incorporated in the cyclen unit. A photo-induced electron transfer (PET) effect that depends on the length of the linker connecting the nitrogen atoms of cyclen to the chromophore is also investigated. The result indicates a linear (log) correlation between the donor-chromophore average distances of the optimized structures calculated by DFT calculations and fluorescence intensities (log I), and the PET effect becomes ineffective at about 12 Å in this system.

Argentivorous molecules bearing two aromatic side-arms: Ag+-π and CH-π interactions in the solid state and in solution.

Seven double-armed cyclens bearing two aromatic side-arms, at the 1- and 7-positions of the cyclens, were prepared via three steps from dimethyl 2,2'-iminodiacetate. The X-ray structures of the Ag(+) complexes and Ag(+)-ion-induced (1)H NMR spectral changes suggest that the two aromatic side-arms cover the Ag(+) ions incorporated in the ligand cavities, as if the aromatic ring "petals" catch the Ag(+) ions in the way a real insectivorous plant (Venus flytrap) catches insects, using two leaves. It is also reported that the CH-π interactions between the aromatic side-arms, as well as the Ag(+)-π interactions, are crucial for double- and tetra-armed cyclens to work as argentivorous molecules.

Chiral Pyridines: Optical Resolution of 1-(2-Pyridyl)- and 1-[6-(2,2'-Bipyridyl)]ethanols by Lipase-Catalyzed Enantioselective Acetylation.

The resolution of racemic 1-(2-pyridyl)ethanols 2a-n, including the 2,2'-bipyridyl and isoquinolyl derivatives, by lipase-catalyzed asymmetric acetylation with vinyl acetate is reported. The reactions were carried out in diisopropyl ether at either room temperature or 60 degrees C using Candida antarctica lipase (CAL) to give (R)-acetate and unreacted (S)-alcohol with excellent enantiomeric purities in good yields. The reaction rate was relatively slow at room temperature for substrates bearing an sp(3)-type carbon at the 6-position on the pyridine ring, such as 2c, 2d, and 2e, and for those bearing 1-hydroxypropyl and allyl groups at the 2-position on the pyridine ring, such as 2l and 2m. In such cases, a higher temperature was required. Thus, when the reaction was conducted at 60 degrees C, it was accelerated 3- to 7-fold without losing the high enantiospecificity. However, the reaction of homoallylic alcohol 2n was not complete, even when the reaction was continued for a longer period of time at 60 degrees C. This enzymatic resolution can be used practically in a wide range of reaction scales from 10 mg to 10 g or more. This catalyst can be used repeatedly with a 5-10% loss of the initial activity with each use.