Supramolecular assembly of group 11 phosphorescent metal complexes for chemosensors of alcohol derivatives

We report on systematic study on vapochromic sensing of ethanol by using phosphorescent trinuclear metal pyrazolate complexes with supramolecular assembly of weak intermolecular metal-metal interactions using 4-(3,5-dimethoxybenzyl)-3,5-dimethyl pyrazole ligand (1) and group 11 metal ions (Cu(I), Ag(I), Au(I)). Upon excitation at 284, the resulting complexes showed emission bands with a peak centered at 616, 473 and 612 nm for 2(Cu), 2(Ag) and 2(Au), respectively. Chemosensor 2(Cu) showed positive response to ethanol vapors in 5 mins by blue-shifting its emission band from 616 to 555 nm and emitting bright orange to green. Otherwise 2(Au) gave shifting from its emission band centered at 612 to 587 nm with Δλ of 25 nm (41%) and color changes from red-orange to light green-orange while 2(Ag) showed quenching in its original emission intensity at 473 nm in 40% with color changes from dark green to less emissive. These results demonstrate that sensing capability of chemosensor 2(Cu) with suitable molecular design of ligand and metal ion in the complex is due to the formation of a weak intermolecular hydrogen bonding interaction of O atom at the methoxy of the benzyl ring with the OH of the vapors at the outside of the molecules.