The chemistry of 2-(2'-pyridyl)-indoles and related compounds.

摘要

Methylation of 2-(2'-pyridyl)-indole (2) provided the corresponding salt 76, which underwent deprotonation to provide the tautomer 86, whose geometry was established. Bridging at the 3,3'-positions led to tautomers having the opposite stereochemistry. The tautomers showed a bathochromic shift in their absorption maxima, strong solvato-chromic dependence, and a weak emission. Their NMR properties were consistent with contributions from a dipolar and uncharged resonance form. The tautomers of pyrrolo[3,2-h]quinoline (4) and its derivatives were prepared. Pyrrolo[3,2-h ]quinolines showed the same NMR and electronic properties as pyrrolo[3,2- h]quinolines, indicating the pyrrole and pyridine nuclei retained appreciable autonomy.; The Ru(II) complexes of 2-(2'-pyridyl)-indole ( 2), pyrrolo[3,2-h]quinoline (4) and their derivatives were prepared. Their NMR properties reflected that the Ru(II) complexes involved deprotonation of the indole or pyrrole NH. Their MLCT absorption maxima appeared at longer wavelengths than the corresponding polypyridyl complexes, which was explained by crystal field theory. Their emission and electrochemical properties were also studied.; The Ru(II) complexes 175--178 were synthesized by microwave heating. Their NMR, electronic and electrochemical properties were studied. The relationship between the MLCT absorption energy and the energy gap (DeltaE1/2) between the first redox couples indicated that Koopman's theorem was obeyed. The [Ru(bpy-d8)2L]2+ complexes, where L = 2-arylphens, were prepared. Their NMR properties in the upfield region of the chemical shift reflected that a pi-stacking effect existed. Molecular modeling of the ligands 162 and 164--166 and their corresponding complexes was carried out. The dinuclear complex 192 existed as a pair of diastereomers. The pi-stacking effect didn't influence the electronic absorption, but did apparently influence the emission behavior.