ic200145h_si_001.pdf (343.87 kB)
Download file

Switching of Molecular Insertion in a Cyclic Molecule via Photo- and Thermal Isomerization

Download (343.87 kB)
journal contribution
posted on 06.06.2011, 00:00 authored by Satoshi Umeki, Shoko Kume, Hiroshi Nishihara
Two new cyclic ligands were synthesized: a ligand with two trans-azobenzene moieties and one bipyridine moiety, trans2-oAB-O13, and a ligand with two trans-azobenzene moieties and two bipyridine moieties, trans2-oAB-bpy. Both ligands underwent reversible trans-cis isomerization at the azobenzene moieties. The mole ratios of the trans2 form:trans-cis form:cis2 form, evaluated by 1H NMR spectroscopy of the photostationary states prepared by 1 h illumination, were 0.13:0.27:0.60 (365 nm irradiation) and 0.41:0.47:0.12 (436 nm irradiation) for oAB-O13, and 0.18:0.12:0.70 (365 nm irradiation) and 0.36:0.43:0.21 (436 nm irradiation) for oAB-bpy. When trans2-oAB-O13 was mixed with Cu(I), both the bipyridine units and the polyether chains coordinated to the copper center. Addition of a noncyclic bipyridine ligand, trans2-oAB-2OH, afforded a bis(bipyridine)copper(I) complex, [Cu(trans2-oAB-O13)(trans2-oAB-2OH)]BF4. The bis(bipyridine) ligand, trans2-oAB-bpy, formed a 1:1 complex with Cu(I), [Cu(trans2-oAB-bpy)]BF4. [Cu(cis2-oAB-bpy)]BF4 did not undergo the ligand substitution reaction with a noncyclic ligand with two azobenzene moieties and one bipyridine moiety, oAB, whereas its thermal isomerization in the presence of oAB caused the formation of [Cu(trans2-oAB-bpy)(trans2-oAB)]BF4, indicating that the isomerization and ligand exchange reactions synchronized via a conformational change of the cyclic ligand.